US20060093568A1

US20060093568A1 - Composition comprising a block polymer and a film-forming agent

Info

Publication number: US20060093568A1
Application number: US10/529,265
Authority: US
Inventors: Xavier Blin; Valerie de La Poterie; Veronique Ferrari
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 2002-09-26
Filing date: 2003-09-26
Publication date: 2006-05-04
Also published as: JP3981129B2; US20060134044A1; JP2006503921A; AU2003283477A8; EP1545442A2; AU2003299071A8; JP3981131B2; WO2004028491A3; AU2003285389A8; US8992903B2; US20060134051A1; WO2004028486A2; AU2003290143A8; WO2004028492A2; EP1545439A2; EP1545436B1; WO2004028485A2; AU2003299069A8; US20060127334A1; WO2004028488A3

Abstract

The present invention provides a cosmetic composition comprising, in a cosmetically acceptable organic liquid medium, at least one film-forming ethylenic linear block polymer, and another film former. The film former may be soluble or dispersible in the said organic liquid medium. The composition may include an aqueous phase, in which case the film former may be soluble or dispersible in the aqueous phase. The invention further provides for the use of the combination of such a block polymer and a film former for enhancing the staying power of the said composition on the keratin materials.

Description

The present invention relates to a cosmetic composition for making up or caring for human bodily and facial skin, the scalp included, the lips or epidermal derivatives of human beings, such as the hair, eyebrows, eyelashes or nails, which comprises a cosmetically acceptable medium comprising a film-forming block polymer in combination with another film former.
The composition may be a loose or compact powder, a foundation, a rouge, an eyeshadow, a concealer, a blusher, a lipstick, a lip balm, a lipgloss, a lip pencil, an eye pencil, a mascara, an eyeliner, a nail varnish or even a body makeup product or a skin colouring product.
Known compositions exhibit poor staying power over time, particularly as regards the colour. This poor staying power is characterized by an alteration in colour (colour change, fading), generally as a result of interaction with the sebum and/or perspiration secreted by the skin, in the case of foundation and of rouge or eyeshadow, or of interaction with the saliva, in the case of lipsticks. This alteration obliges the user to apply fresh makeup at frequent intervals, which may constitute a loss of time.
An improvement in staying power, particularly that of lipsticks, can be obtained by combining a volatile oil with a film-forming polymer, such as silicone resins. The resultant staying power properties, however, remain below consumer expectations.
There continues to be a need for a cosmetic product which leads to a deposit on keratin materials, in particular a makeup result, having good staying power.
The composition of the invention may in particular constitute a product for making up the body, the lips or the epidermal derivatives of human beings which has, in particular, non-therapeutic treatment and/or care properties. It constitutes in particular a lipstick or a lipgloss, a rouge or eyeshadow, a tattooing product, a mascara, an eyeliner, a nail varnish, an artificial skin-tanning product or a hair colouring or haircare product.
Surprisingly the inventors have found that, by combining a specific block polymer with a known film former, cosmetic compositions are obtained which lead to deposits, on keratin materials, whose staying power is superior to that of conventional compositions containing film formers.
More specifically the invention provides a cosmetic composition comprising an organic liquid medium, at least one film-forming ethylenic linear block polymer and at least one other film former.
In particular the invention provides a cosmetic composition comprising an organic liquid medium, at least one film-forming ethylenic linear block polymer and at least one other film former which is soluble in the organic liquid medium.
The invention also provides a cosmetic composition comprising an organic liquid medium, at least one film-forming ethylenic linear block polymer and at least one other, water-soluble film former.
The invention further provides a cosmetic composition comprising an organic liquid medium, at least one film-forming ethylenic linear block polymer and at least one aqueous dispersion of film-forming-polymer particles.
The invention further provides a cosmetic composition comprising an organic liquid medium, at least one film-forming ethylenic linear block polymer and at least one non-aqueous dispersion of film-forming polymer particles.
The film-forming ethylenic linear block polymer is advantageously non-elastomeric. The film-forming ethylenic linear block polymer is advantageously free from styrene units.
The invention also relates to a method of making up the skin and/or the lips and/or the epidermal derivatives which consists in applying to the skin and/or the lips and/or the epidermal derivatives the composition as defined above.
The composition according to the invention may be applied to the skin of the face, the scalp and the body, the mucosae such as the lips, the inside of the lower eyelids, and the epidermal derivatives such as the nails, eyebrows, hair, eyelashes, and even body hair.
Preferably the composition according to the invention is not a rinse-off composition.
The invention likewise relates to the cosmetic use of the composition defined above for enhancing the staying power of makeup on the skin and/or the lips and/or the epidermal derivatives.
In particular, in the case of an eyelash-coating composition or mascara, a composition of this kind makes it possible to obtain, following application to the eyelashes, a makeup film exhibiting good staying power, particularly with respect to water, during bathing or showering for example, to rubbing, particularly with the fingers, and/or to tears, perspiration or sebum.
The invention provides finally for the use of a film former in a composition comprising a block polymer as described above for the purpose of obtaining a composition which has good texture, is easy to apply and leads to a deposit with good staying power on the lips and/or the epidermal derivatives.
Block Polymer:
The composition according to the present invention comprises at least one block polymer. By “block” polymer is meant a polymer comprising at least 2 distinct blocks, preferably at least 3 distinct blocks.
According to one embodiment the block polymer of the composition according to the invention is an ethylenic polymer. By “ethylenic” polymer is meant a polymer obtained by polymerizing monomers comprising an ethylenic unsaturation.
According to one embodiment the block polymer of the composition according to the invention is a linear polymer. By opposition, a polymer having a non-linear structure is, for example, a polymer having a branched, starburst, graft or other structure.
According to one embodiment the block polymer of the composition according to the invention is a film-forming polymer. By “film-forming” polymer is meant a polymer capable of forming, by itself or in the presence of an auxiliary film-forming agent, a continuous and adherent film on a support, particularly on keratin materials.
According to one embodiment the block polymer of the composition according to the invention is a non-elastomeric polymer.
By “non-elastomeric polymer” is meant a polymer which, when subjected to a stress intended to stretch it (for example by 30% relative to its initial length), does not return to a length substantially identical to its initial length when the stress ceases.
More specifically the term “non-elastomeric polymer” denotes a polymer having an instantaneous recovery R_i<50% and a retarded recovery R_2h<70% after having undergone 30% elongation. Preferably R_iis <30% and R_2his <50%.
More specifically the non-elastomeric character of the polymer is determined in accordance with the following protocol:
A polymer film is prepared by pouring a solution of the polymer into a Teflon-coated mould and then drying it for 7 days in an environment controlled at 23±50° C. and 50±10% relative humidity.
This gives a film approximately 100 μm thick, from which rectangular specimens are cut (using a punch, for example) 15 mm wide and 80 mm long.
This sample is subjected to a tensile stress by means of an apparatus sold under the reference Zwick, under the same temperature and humidity conditions as for drying.
The specimens are stretched at a speed of 50 mm/min, and the distance between the jaws is 50 mm, corresponding to the initial length (l₀) of the specimen.
The instantaneous recovery Ri is determined as follows:
the specimen is stretched by 30% (ε_max), i.e. about 0.3 times its initial length (l₀);
the stress is released by applying a return speed equal to the tensile speed, i.e. 50 mm/min, and the residual elongation of the specimen is measured as a percentage, after return to zero stress (ε_i).
The instantaneous recovery in % (R_i) is given by the formula below:
R _i=(ε_max−ε_i)/ε_max)×100
To determine the retarded recovery the residual elongation of the specimen is measured as a percentage (ε_2h) 2 hours after return to zero stress.
The retarded recovery in % (R_2h) is given by the formula below:
R _2h=(ε_max−ε_2h)/ε_max)×100
Purely by way of indication, a polymer according to one embodiment of the invention possesses an instantaneous recovery R_iof 10% and a retarded recovery R_2hof 30%.
According to another embodiment the block polymer of the composition according to the invention does not include a styrene unit. By polymer free from styrene units is meant a polymer containing less than 10%, preferably less than 5%, preferably less than 2%, more preferably less than 1% by weight i) of styrene unit of formula —CH(C₆H₅)—CH₂— or ii) of substituted styrene unit, for example methylstyrene, chlorostyrene or chloromethylstyrene.
According to one embodiment the block polymer of the composition according to the invention is obtained from aliphatic ethylenic monomers. By aliphatic monomer is meant a monomer containing no aromatic group.
According to one embodiment the block polymer is an ethylenic polymer obtained from aliphatic ethylenic monomers comprising a carbon-carbon double bond and at least one ester group —COO— or amide group —CON—. The ester group may be bonded to one of the two unsaturated carbons via the carbon atom or the oxygen atom. The amide group may be bonded to one of the two unsaturated carbons via the carbon atom or the nitrogen atom.
According to one mode of implementation the block polymer comprises at least one first block and at least one second block.
By “at least” one block is meant one or more blocks.
It is specified that, in the text above and below, the terms “first” and “second” blocks in no way condition the order of the said blocks (or sequences) in the structure of the polymer.
According to one mode of implementation the block polymer comprises at least one first block and at least one second block which have different glass transition temperatures (Tgs).
In this mode of implementation the first and second blocks may be connected to one another by an intermediate segment having a glass transition temperature between the glass transition temperatures of the first and second blocks.
According to one mode of implementation the block polymer comprises at least one first block and at least one second block connected to one another by an intermediate segment comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block.
Preferably the intermediate block is obtained essentially from constituent monomers of the first block and of the second block.
By “essentially” is meant to an extent of at least 85%, preferably at least 90%, more preferably 95% and more preferably still 100%.
Advantageously the intermediate segment comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block of the polymer is a random polymer.
According to one mode of implementation the block polymer comprises at least one first block and at least one second block which are incompatible in the organic liquid medium of the composition of the invention.
By “blocks incompatible with one another” is meant that the mixture formed from the polymer corresponding to the first block and from the polymer corresponding to the second block is not miscible in the organic liquid that is in a majority by weight in the organic liquid medium of the composition, at ambient temperature (25° C.) and atmospheric pressure (10⁵Pa), for a polymers mixture content greater than or equal to 5% by weight, relative to the total weight of the mixture (polymers and majority organic liquid), with the provisos that
i) the said polymers are present in the mixture in an amount such that the respective weight ratio ranges from 10/90 to 90/10, and that
ii) each of the polymers corresponding to the first and second blocks has an average molecular mass (by weight or by number) equal to that of the block polymer +/−15%.
In the case where the organic liquid medium comprises a mixture of organic liquids, should two or more liquids be present in identical mass proportions, the said polymers mixture is not miscible in at least one of them.
In the case where the organic liquid medium comprises a single organic liquid, the said liquid, quite obviously, constitutes the liquid that is in a majority by weight.
By “organic liquid medium” is meant a medium comprising at least one organic liquid, in other words at least one organic compound which is liquid at ambient temperature (25° C.) and atmospheric pressure (10⁵Pa). According to one mode of implementation the majority liquid of the organic liquid medium is a volatile or non-volatile oil (fat). Preferably the organic liquid is cosmetically acceptable (acceptable tolerance, toxicology and feel). The organic liquid medium is cosmetically acceptable in the sense that it is compatible with keratin materials, such as the oils or organic solvents commonly employed in cosmetic compositions.
According to one mode of implementation the majority liquid of the organic liquid medium is the polymerization solvent or one of the polymerization solvents of the block polymer, as are described below.
By polymerization solvent is meant a solvent or a mixture of solvents. The polymerization solvent may be selected in particular from ethyl acetate, butyl acetate, alcohols such as isopropanol and ethanol, aliphatic alkanes such as isododecane, and mixtures thereof. Preferably the polymerization solvent is a mixture of butyl acetate and isopropanol, or isododecane.
Generally speaking, the block polymer may be incorporated into the composition at a high solids content, typically more than 10%, more than 20% and more preferably more than 30% and more preferably still more than 45% by weight relative to the total weight of the composition, while being easy to formulate.
Preferentially the block polymer does not include silicon atoms in its skeleton. By “skeleton” is meant the main chain of the polymer, as opposed to the pendent side chains.
Preferably the polymer according to the invention is not water-soluble, which is to say that the polymer is not soluble in water or in a mixture of water and linear or branched lower monoalcohols having 2 to 5 carbon atoms, such as ethanol, isopropanol or n-propanol, without a change in pH, at an active substance content of at least 1% by weight, at ambient temperature (25° C.).
According to one mode of implementation the block polymer has a polydispersity index I of greater than 2.
Advantageously the block polymer used in the compositions according to the invention has a polydispersity index I of greater than 2, ranging for example from 2 to 9, preferably greater than or equal to 2.5, ranging for example from 2.5 to 8, and better still greater than or equal to 2.8, and in particular ranging from 2.8 to 6.
The polydispersity index I of the polymer is equal to the ratio of the weight-average mass Mw to the number-average mass Mn.
The weight-average (Mw) and number-average (Mn) molar masses are determined by liquid chromatography by gel permeation (THF solvent, calibration curve established with standards of linear polystyrene, refractometric detector).
The weight-average mass (Mw) of the block polymer is preferably less than or equal to 300 000, and ranges for example from 35 000 to 200 000, better still from 45 000 to 150 000.
The number-average mass (Mn) of the block polymer is preferably less than or equal to 70 000, and ranges for example from 10 000 to 60 000, better still from 12 000 to 50 000.
Each block or sequence of the block polymer is obtained from one type of monomer or from two or more different types of monomers.
This signifies that each block may be composed of a homopolymer or of a copolymer; this copolymer, constituting the block, may in turn be random or alternating.
The glass transition temperatures indicated for the first and second blocks may be theoretical Tgs determined from the theoretical Tgs of the constituent monomers of,each of the blocks, which can be found in a reference manual such as the Polymer Handbook, 3rd ed., 1989, John Wiley, according to the following relationship, called Fox's Law: $\frac{1 / Tg = \sum ({\overline{ω}}_{i} / {Tg}_{i})}{i},$
{overscore (ω)}_ibeing the mass fraction of the monomer i in the block in question and Tg_ibeing the glass transition temperature of the homopolymer of the monomer i.
Unless indicated otherwise, the Tgs indicated for the first and second blocks in the present specification are theoretical Tgs.
The difference between the glass transition temperatures of the first and second blocks is generally greater than 10° C., preferably greater than 20° C. and more preferably greater than 30° C.
In particular the block polymer comprises at least one first block and at least one second block such that the first block may be selected from:
a) a block with a Tg of greater than or equal to 40° C.,
b) a block with a Tg of less than or equal to 20° C.,
c) a block with a Tg of between 20 and 40° C.,
and the second block may be selected from a category a), b) or c) different from the first block.
In the present invention, the expression “between . . . and . . . ” is intended to denote a range of values for which the limits mentioned are excluded, and the expression “from . . . to . . . ” and “ranging from . . . to . . . ” is intended to denote a range of values for which the limits are included.
a) Block with a Tg of Greater Than or Equal to 40° C.
The block with a Tg of greater than or equal to 40° C. has, for example, a Tg ranging from 40 to 150° C., preferably greater than or equal to 50° C., ranging for example from 50° C. to 120° C., and better still greater than or equal to 60° C., ranging for example from 60° C. to 120° C.
The block with a Tg of greater than or equal to 40° C. may be a homopolymer or a copolymer.
The block with a Tg of greater than or equal to 40° C. may be obtained totally or partly from one or more monomers which are such that the homopolymer prepared from these monomers has a glass transition temperature of greater than or equal to 40° C.
In the case where this block is a homopolymer, it is obtained from monomers which are such that the homopolymers prepared from these monomers have glass transition temperatures of greater than or equal to 40° C. This first block may be a homopolymer composed of a single type of monomer (for which the Tg of the corresponding homopolymer is greater than or equal to 40° C.).
In the case where the first block is a copolymer, it may be obtained totally or partly from one or more monomers, the nature and concentration of which are selected such that the Tg of the resulting copolymer is greater than or equal to 40° C. The copolymer may comprise, for example:
monomers which are such that the homopolymers prepared from these monomers have Tgs of greater than or equal to 40° C., for example a Tg ranging from 40 to 150° C., preferably greater than or equal to 50° C., ranging for example from 50° C. to 120° C., and better still greater than or equal to 60° C., ranging for example from 60° C. to 120° C., and
monomers which are such that the homopolymers prepared from these monomers have Tgs of less than 40° C., selected from monomers with a Tg of between 20 to 40° C. and/or monomers with a Tg of less than or equal to 20° C., for example a Tg ranging from −100 to 20° C., preferably less than 15° C., especially ranging from −80° C. to 15° C. and better still less than 10° C., for example ranging from −50° C. to 0° C., as described later.
The monomers whose homopolymers have a glass transition temperature of greater than or equal to 40° C. are selected, preferably, from the following monomers, also known as principal monomers:
methacrylates of formula CH₂═C(CH₃)—COOR₁in which R₁represents a linear or branched unsubstituted alkyl group containing from 1 to 4 carbon atoms, such as a methyl, ethyl, propyl or isobutyl group, or R₁represents a C₄to C₁₂cycloalkyl group;
acrylates of formula CH₂═CH—COOR₂in which R₂represents a C₄to C₁₂cycloalkyl group, such as isobornyl acrylate or a tert-butyl group;
(meth)acrylamides of formula:

where R₇and R₈, which are identical or different, each represent a hydrogen atom or a linear or branched C₁to C₁₂alkyl group, such as an n-butyl, t-butyl, isopropyl, isohexyl, isooctyl or isononyl group; or R₇represents H and R₈represents a 1,1-dimethyl-3-oxobutyl group and R′ denotes H or methyl. Examples of monomers that may be mentioned include N-butylacrylamide, N-t-butylacrylamide, N-isopropylacrylamide, N,N-dimethylacrylamide and N,N-dibutylacrylamide;
and mixtures thereof.
Principal monomers that are particularly preferred are methyl methacrylate, isobutyl (meth)acrylate and isobornyl (meth)acrylate, and mixtures thereof.
b) Block with a Tg of Less Than or Equal to 20° C.
The block with a Tg of less than or equal to 20° C. has, for example, a Tg ranging from −100 to 20° C., preferably less than or equal to 15° C., especially ranging from −80° C. to 15° C. and better still less than or equal to 10° C., for example ranging from −50° C. to 0° C.
The block with a Tg of less than or equal to 20° C. may be a homopolymer or a copolymer.
The block with a Tg of less than or equal to 20° C. may be obtained totally or partly from one or more monomers which are such that the homopolymer prepared from these monomers has a glass transition temperature of less than or equal to 20° C.
In the case where this block is a homopolymer, it is obtained from monomers which are such that the homopolymers prepared from these monomers have glass transition temperatures of less than or equal to 20° C. This second block may be a homopolymer -composed of a single type of monomer (for which the Tg of the corresponding homopolymer is less than or equal to 20° C.).
In the case where the block with a Tg of less than or equal to 20° C. is a copolymer, it may be obtained totally or partly from one or more monomers, the nature and concentration of which are selected such that the Tg of the resulting copolymer is less than or equal to 20° C.
It may comprise, for example
one or more monomers whose corresponding homopolymer has a Tg of less than or equal to 20° C., for example a Tg ranging from −100° C. to 20° C., preferably less than 15° C., especially ranging from −80° C. to 15° C. and better still less than 10° C., for example ranging from −50° C. to 0° C., and
one or more monomers whose corresponding homopolymer has a Tg of greater than 20° C., such as monomers with a Tg of greater than or equal to 40° C., for example a Tg ranging from 40 to 150° C., preferably greater than or equal to 50° C., ranging for example from 50° C. to 120° C. and better still greater than or equal to 60° C., ranging for example from 60° C. to 120° C. and/or monomers with a Tg of between 20 and 40° C., as described above.
Preferably the block with a Tg of less than or equal to 20° C. is a homopolymer.
The monomers whose homopolymer has a Tg of less than or equal to 20° C. are selected, preferably, from the following monomers, or principal monomer:
acrylates of formula CH₂═CHCOOR₃, R₃representing a linear or branched C₁to C₁₂unsubstituted alkyl group, with the exception of the tert-butyl group, in which one or more heteroatoms selected from O, N and S is (are) optionally intercalated;
methacrylates of formula CH₂═C(CH₃)—COOR₄, R₄representing a linear or branched C₆to C₁₂unsubstituted alkyl group, in which one or more hetero-atoms selected from O, N and S is (are) optionally intercalated;
vinyl esters of formula R₅—CO—O—CH═CH₂where R₅represents a linear or branched C₄to C₁₂alkyl group;
C₄to C₁₂alkyl vinyl ethers;
N—(C₄to C₁₂alkyl) acrylamides, such as N-octylacrylamide;
and mixtures thereof.
The principal monomers that are particularly preferred for the block with a Tg of less than or equal to 20° C. are alkyl acrylates in which the alkyl chain contains from 1 to 10 carbon atoms, with the exception of the tert-butyl group, such as methyl acrylate, isobutyl acrylate and 2-ethylhexyl acrylate, and mixtures thereof.
c) Block with a Tg of Between 20 and 40° C.
The block which has a Tg of between 20 and 40° C. may be a homopolymer or a copolymer.
The block with a Tg of between 20 and 40° C. may be obtained totally or partly from one or more monomers which are such that the homopolymer prepared from these monomers has a glass transition temperature of between 20 and 40° C.
The block with a Tg of between 20 and 40° C. may be obtained totally or partly from monomers which are such that the corresponding homopolymer has a Tg of greater than or equal to 40° C. and from monomers which are such that the corresponding homopolymer has a Tg of less than or equal to 20° C.
In the case where this block is a homopolymer, it is obtained from monomers (or principal monomers) which are such that the homopolymers prepared from these monomers have glass transition temperatures of between 20 and 40° C. This first block may be a homopolymer composed of a single type of monomer (for which the Tg of the corresponding homopolymer ranges from 20° C. to 40° C.).
The monomers whose homopolymer has a glass transition temperature of between 20 and 40° C. are selected, preferably, from n-butyl methacrylate, cyclodecyl acrylate, neopentyl acrylate and isodecylacrylamide, and mixtures thereof.
In the case where the block with a Tg of between 20 and 40° C. is a copolymer, it is obtained totally or partly from one or more monomers (or principal monomers) the nature and concentration of which are selected such that the Tg of the resulting copolymer is between 20 and 40° C.
Advantageously the block with a Tg of between 20 and 40° C. is a copolymer obtained totally or partly from:
principal monomers whose corresponding homopolymer has a Tg of greater than or equal to 40° C., for example a Tg ranging from 40° C. to 150° C., preferably greater than or equal to 50° C., ranging for example from 50 to 120° C. and better still greater than or equal to 60° C., ranging for example from 60° C. to 120° C., as described above; and/or
principal monomers whose corresponding homopolymer has a Tg of less than or equal to 20° C., for example a Tg ranging from −100 to 20° C., preferably less than or equal to 15° C., especially ranging from −80° C. to 15° C. and better still less than or equal to 10° C., for example ranging from −50° C. to 0° C., as described above, the said monomers being selected such that the Tg of the copolymer forming the first block is between 20 and 40° C.
Such principal monomers are selected, for example, from methyl methacrylate, isobornyl acrylate and methacrylate, butyl acrylate and 2-ethylhexyl acrylate, and mixtures thereof.
Preferably the proportion of the second block with a Tg of less than or equal to 20° C. ranges from 10% to 85%, better still from 20% to 70% and even better still from 20% to 50% by weight of the polymer.
Preferably each of the first and second blocks comprises at least one monomer selected from acrylic acid, the esters of acrylic acid, (meth)acrylic acid, the esters of (meth)acrylic acid, and mixtures thereof.
Advantageously each of the first and second blocks is obtained totally from at least one monomer selected from acrylic acid, the esters of acrylic acid, (meth)acrylic acid, the esters of (meth)acrylic acid, and mixtures thereof.
However, each of the blocks may contain in minority proportion at least one constituent monomer of the other block.
Thus the first block may contain at least one constituent monomer of the second block, and vice versa.
Each of the first and/or second blocks may comprise, in addition to the monomers indicated above, one or more other monomers known as additional monomers, which are different from the principal monomers mentioned above.
The nature and amount of this or these additional monomer(s) are selected such that the block in which they are present has the desired glass transition temperature.
This additional monomer is selected, for example, from:
a) hydrophilic monomers such as:
ethylenically unsaturated monomers comprising at least one carboxylic or sulphonic acid function, for instance: acrylic acid, methacrylic acid, crotonic acid, maleic anhydride, itaconic acid, fumaric acid, maleic acid, acrylamidopropanesulphonic acid, vinylbenzoic acid, vinylphosphoric acid, and salts thereof;
ethylenically unsaturated monomers comprising at least one tertiary amine function, for instance 2-vinylpyridine, 4-vinylpyridine, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate and dimethylaminopropylmethacrylamide, and salts thereof;
methacrylates of formula CH₂═C(CH₃)—COOR₆in which R₆represents a linear or branched alkyl group containing from 1 to 4 carbon atoms, such as a methyl, ethyl, propyl or isobutyl group, the said alkyl group being substituted by one or more substituents selected from hydroxyl groups (for instance 2-hydroxypropyl methacrylate and 2-hydroxyethyl methacrylate) and halogen atoms (Cl, Br, I or F), such as trifluoroethyl methacrylate;
methacrylates of formula CH₂═C(CH₃)—COOR₉, R₉representing a linear or branched C₆to C₁₂alkyl group in which one or more heteroatoms selected from O, N and S is (are) optionally intercalated, the said alkyl group being substituted by one or more substituents selected from hydroxyl groups and halogen atoms (Cl, Br, I or F);
acrylates of formula CH₂═CHCOOR₁₀, R₁₀representing a linear or branched C₁to C₁₂alkyl group substituted by one or more substituents selected from hydroxyl groups and halogen atoms (Cl, Br, I or F), such as 2-hydroxypropyl acrylate and 2-hydroxyethyl acrylate, or R₁₀represents a C₁to C₁₂alkyl-O-POE (polyoxyethylene) with repetition of the oxyethylene unit from 5 to 30 times, for example methoxy-POE, or R₁₀represents a polyoxyethylenated group comprising from 5 to 30 ethylene oxide units;
b) ethylenically unsaturated monomers comprising one or more silicon atoms, such as methacryloxypropyltrimethoxysilane and methacryloxypropyltris(trimethylsiloxy)silane;
and mixtures thereof.
Additional monomers that are particularly preferred are acrylic acid, methacrylic acid and trifluoroethyl methacrylate, and mixtures thereof.
According to one embodiment, each of the first and second blocks of the block polymer comprises at least one monomer selected from esters of (meth)acrylic acid and optionally at least one additional monomer such as (meth)acrylic acid, and mixtures thereof.
According to another embodiment, each of the first and second blocks of the block polymer is obtained totally from at least one monomer selected from esters of (meth)acrylic acid and optionally at least one additional monomer such as (meth)acrylic acid, and mixtures thereof.
According to one preferred embodiment, the block polymer is a non-silicone polymer, i.e. a polymer free of silicon atoms.
This or these additional monomer(s) generally represent(s) an amount of less than or equal to 30% by weight, for example from 1% to 30% by weight, preferably from 5% to 20% by weight and more preferably from 7% to 15% by weight, relative to the total weight of the first and/or second blocks.
The block polymer may be obtained by free-radical solution polymerization according to the following preparation process:
a portion of the polymerization solvent is introduced into a suitable reactor and heated until the adequate temperature for the polymerization is reached (typically between 60 and 120° C.),
once this temperature is reached, the constituent monomers of the first block are introduced in the presence of a portion of the polymerization initiator,
after a time T corresponding to a maximum degree of conversion of 90%, the constituent monomers of the second block and the rest of the initiator are introduced,
the mixture is left to react for a time T′ (ranging from 3 to 6 hours), after which the mixture is cooled to ambient temperature,
the polymer in solution in the polymerization solvent is obtained.

First Embodiment

According to a first embodiment, the block polymer comprises a first block with a Tg of greater than or equal to 40° C., as described above in a), and a second block with a Tg of less than or equal to 20° C., as described above in b).
Preferably the first block with a Tg of greater than or equal to 40° C. is a copolymer obtained from monomers which are such that the homopolymer prepared from these monomers has a glass transition temperature of greater than or equal to 40° C., such as the monomers described above.
Advantageously the second block with a Tg of less than or equal to 20° C. is a homopolymer obtained from monomers which are such that the homopolymer prepared from these monomers has a glass transition temperature of less than or equal to 20° C., such as the monomers described above.
Preferably the proportion of the block with a Tg of greater than or equal to 40° C. ranges from 20% to 90%, better still from 30% to 80% and even better still from 50% to 70% by weight of the polymer.
Preferably the proportion of the block with a Tg of less than or equal to 20° C. ranges from 5% to 75%, preferably from 15% to 50% and better still from 25% to 45% by weight of the polymer.
Thus, according to a first variant, the polymer according to the invention-may comprise:
a first block with a Tg of greater than or equal to 40° C., for example having a Tg ranging from 70 to 110° C., which is a methyl methacrylate/acrylic acid copolymer,
a second block with a Tg of less than or equal to 20° C., for example ranging from 0 to 20° C., which is a methyl acrylate homopolymer, and
an intermediate block which is a methyl methacrylate/acrylic acid/methyl acrylate copolymer.
According to a second variant, the polymer according to the invention may comprise:
a first block with a Tg of greater than or equal to 40° C., for example ranging from 70 to 100° C., which is a methyl methacrylate/acrylic acid/trifluoroethyl methacrylate copolymer,
a second block with a Tg of less than or equal to 20° C., for example ranging from 0 to 20° C., which is a methyl acrylate homopolymer, and
an intermediate block which is a methyl methacrylate/acrylic acid/methyl acrylate/trifluoro-ethyl methacrylate random copolymer.
According to a third variant, the polymer according to the invention may comprise:
a first block with a Tg of greater than or equal to 40° C., for example ranging from 85 to 115° C., which is an isobornyl acrylate/isobutyl methacrylate copolymer,
a second block with a Tg of less than or equal to 20° C., for example ranging from −85 to −55° C., which is a 2-ethylhexyl acrylate homopolymer, and
an intermediate block which is an isobornyl acrylate/isobutyl methacrylate/2-ethylhexyl acrylate random copolymer.
According to a fourth variant, the polymer according to the invention may comprise:
a first block with a Tg of greater than or equal to 40° C., for example ranging from 85 to 115° C., which is an isobornyl acrylate/methyl methacrylate copolymer,
a second block with a Tg of less than or equal to 20° C., for example ranging from −85 to −55° C., which is a 2-ethylhexyl acrylate homopolymer, and
an intermediate block which is an isobornyl acrylate/methyl methacrylate/2-ethylhexyl acrylate random copolymer.
According to a fifth variant, the polymer according to the invention may comprise:
a first block with a Tg of greater than or equal to 40° C., for example ranging from 95 to 125° C., which is an isobornyl acrylate/isobornyl methacrylate copolymer,
a second block with a Tg of less than or equal to 20° C., for example ranging from −85 to −55° C., which is a 2-ethylhexyl acrylate homopolymer, and
an intermediate block which is an isobornyl acrylate/isobornyl methacrylate/2-ethylhexyl acrylate random copolymer.
According to a sixth variant, the polymer according to the invention may comprise:
a first block with a Tg of greater than or equal to 40° C., for example ranging from 85 to 115° C., which is an isobornyl methacrylate/isobutyl methacrylate copolymer,
a second block with a Tg of less than or equal to 20° C., for example ranging from −35 to −5° C., which is an isobutyl acrylate homopolymer, and
an intermediate block which is an isobornyl methacrylate/isobutyl methacrylate/isobutyl acrylate random copolymer.
According to a seventh variant, the polymer according to the invention may comprise:
a first block with a Tg of greater than or equal to 40° C., for example ranging from 95 to 125° C., which is an isobornyl acrylate/isobornyl methacrylate copolymer,
a second block with a Tg of less than or equal to 20° C., for example ranging from −35 to −5° C., which is an isobutyl acrylate homopolymer, and
an intermediate block which is an isobornyl acrylate/isobornyl methacrylate/isobutyl acrylate random copolymer.
According to an eighth variant, the polymer according to the invention may comprise:
a first block with a Tg of greater than or equal to 40° C., for example ranging from 60 to 90° C., which is an isobornyl acrylate/isobutyl methacrylate copolymer,
a second block with a Tg of less than or equal to 20° C., for example ranging from −35 to −5° C., which is an isobutyl acrylate homopolymer, and
an intermediate block which is an isobornyl acrylate/isobutyl methacrylate/isobutyl acrylate random copolymer.
The examples which follow illustrate, non-limitatively, polymers corresponding to this first embodiment.
The amounts are expressed in grams.

EXAMPLE 1

Preparation of a poly(isobornyl acrylate/methyl methacrylate/2-ethylhexyl acrylate) polymer

100 g of isododecane are introduced into a 1 litre reactor and then the temperature is raised so as to go from ambient temperature (₂₅° C.) to 90° C. over 1 hour.
Subsequently there are added, at 90° C. and over 1 hour, 150 g of isobornyl acrylate, 60 g of methyl methacrylate, 110 g of isododecane and 1.8 g of 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (Trigonox® 141 from Akzo Nobel).
The mixture is held at 90° C. for 1.5 h.
Subsequently there are introduced into the above mixture, still at 90° C. and over 30 minutes, 90 g of 2-ethylhexyl acrylate, 90 g of isododecane and 1.2 g of 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane.
The mixture is held at 90° C. for 3 hours and then the whole is cooled.
This gives a solution containing 50% polymer active substance in isododecane.
A polymer is obtained which comprises a first, poly(isobornyl acrylate/methyl methacrylate) block with a Tg of 100° C., a second, poly-2-ethylhexyl acrylate block with a Tg of −70° C., and an intermediate block which is an isobornyl acrylate/methyl methacrylate/2-ethylhexyl acrylate random polymer.
This polymer has a weight-average mass of 76 500 and a number-average mass of 22 000, giving a polydispersity index I of 3.48.

EXAMPLE 2

Preparation of a poly(isobornyl acrylate/isobornyl methacrylate/2-ethylhexyl acrylate) polymer

100 g of isododecane are introduced into a 1 litre reactor and then the temperature is raised so as to go from ambient temperature (25° C.) to 90° C. over 1 hour.
Subsequently there are added, at 90° C. and over 1 hour, 105 g of isobornyl acrylate, 105 g of isobornyl methacrylate, 110 g of isododecane and 1.8 g of 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (Trigonox® 141 from Akzo Nobel).
The mixture is held at 90° C. for 1.5 h.
Subsequently there are introduced into the above mixture, still at 90° C. and over 30 minutes, 90 g of 2-ethylhexyl acrylate, 90 g of isododecane and 1.2 g of 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane.
The mixture is held at 90° C. for 3 hours and then the whole is cooled.
This gives a solution containing 50% polymer active substance in isododecane.
A polymer is obtained which comprises a first, poly(isobornyl acrylate/isobornyl methacrylate) block with a Tg of 110° C., a second, poly-2-ethylhexyl acrylate block with a Tg of −70° C., and an intermediate block which is an isobornyl acrylate/isobornyl methacrylate/2-ethylhexyl acrylate random polymer.
This polymer has a weight-average mass of 103 900 and a number-average mass of 21 300, giving a polydispersity index I of 4.89.

EXAMPLE 3

Preparation of a poly(isobornyl acrylate/isobutyl methacrylate/isobutyl acrylate) polymer

100 g of isododecane are introduced into a 1 litre reactor and then the temperature is raised so as to go from ambient temperature (25° C.) to 90° C. over 1 hour.
Subsequently there are added, at 90° C. and over 1 hour, 120 g of isobornyl acrylate, 90 g of isobutyl methacrylate, 110 g of isododecane and 1.8 g of 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (Trigonox® 141 from Akzo Nobel).
The mixture is held at 90° C. for 1.5 h.
Subsequently there are introduced into the above mixture, still at 90° C. and over 30 minutes, 90 g of isobutyl acrylate, 90 g of isododecane and 1.2 g of 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane.
The mixture is held at 90° C. for 3 hours and then the whole is cooled.
This gives a solution containing 50% polymer active substance in isododecane.
A polymer is obtained which comprises a first, poly(isobornyl acrylate/isobutyl methacrylate) block with a Tg of 75° C., a second, polyisobutyl acrylate block with a Tg of −20° C., and an intermediate block which is an isobornyl acrylate/isobutyl methacrylate/isobutyl acrylate random polymer.
This polymer has a weight-average mass of 144 200 and a number-average mass of 49 300, giving a polydispersity index I of 2.93.

Second Embodiment

According to a second embodiment, the block polymer comprises a first block with a glass transition temperature (Tg) of between 20 and 40° C., in accordance with the blocks described in c), and a second block with a glass transition temperature of less than or equal to 20° C., as described above in b), or a glass transition temperature of greater than or equal to 40° C., as described in a) above.
Preferably the proportion of the first block with a Tg of between 20 and 40° C. ranges from 10% to 85%, better still from 30% to 80% and even better still from 50% to 70% by weight of the polymer.
When the second block is a block with a Tg of greater than or equal to 40° C., it is preferably present in a proportion ranging from 10% to 85% by weight, better still from 20% to 70% and even better still from 30% to 70% by weight of the polymer.
When the second block is a block with a Tg of less than or equal to 20° C., it is preferably present in a proportion ranging from 10% to 85% by weight, better still from 20% to 70% and even better still from 20% to 50% by weight of the polymer.
Preferably the first block with a Tg of between 20 and 40° C. is a copolymer obtained from monomers which are such that the corresponding homopolymer has a Tg of greater than or equal to 40° C., and from monomers which are such that the corresponding homopolymer has a Tg of less than or equal to 20° C.
Advantageously the second block with a Tg of less than or equal to 20° C. or with a Tg of greater than or equal to 40° C. is a homopolymer.
Thus, according to a first variant of this second embodiment, the block polymer may comprise:
a first block with a Tg of between 20 and 40° C., for example with a Tg of 25 to 39° C., which is a copolymer comprising at least one methyl acrylate monomer, at least one methyl methacrylate monomer and at least one acrylic acid monomer,
a second block with a Tg of greater than or equal to 40° C., for example ranging from 85 to 125° C., which is a homopolymer composed of methyl methacrylate monomers, and
an intermediate block comprising at least one methyl acrylate or methyl methacrylate monomer, and
an intermediate block comprising methyl methacrylate, at least one acrylic acid monomer and at least one methyl acrylate monomer.
According to a second variant of this second embodiment, the block polymer may comprise:
a first block with a Tg of between 20 and 40° C., for example with a Tg of 21 to 39° C., which is a copolymer comprising isobornyl acrylate/isobutyl methacrylate/2-ethylhexyl acrylate,
a second block with a Tg of less than or equal to 20° C., for example ranging from −65 to −35° C., which is a methyl methacrylate homopolymer, and
an intermediate block which is an isobornyl acrylate/isobutyl methacrylate/2-ethylhexyl acrylate random copolymer.
According to a third variant of this second embodiment, the block polymer may comprise:
a first block with a Tg of between 20 and 40° C., for example with a Tg of from 21 to 39° C., which is an isobornyl acrylate/methyl acrylate/acrylic acid copolymer,
a second block with a Tg of greater than or equal to 40° C., for example ranging from 85 to 115° C., which is an isobornyl acrylate homopolymer, and
an intermediate block which is an isobornyl acrylate/methyl acrylate/acrylic acid random copolymer.
The composition according to the invention contains preferably from 0.1% to 60% by weight of polymer active substance (or polymer solids), preferably from 0.5% to 50% by weight and more preferably from 1% to 40% by weight.
Film Former
The composition of the invention also includes at least one film former, which may be an organic or inorganic polymer. The film former, when it is an organic polymer, is not a film-forming ethylenic linear block polymer as described above.
In one embodiment, the film-forming organic polymer is at least one polymer selected from the group consisting of:
film-forming polymers which are soluble in the organic liquid medium, in particular fat-soluble polymers, when the organic liquid medium comprises at least one oil,
film-forming polymers which are dispersible in the organic liquid solvent medium, in particular polymers in the form of non-aqueous dispersions of polymer particles, preferably dispersions in silicone oils or hydrocarbon-based oils; in one embodiment, the non-aqueous dispersions of polymer comprise polymer particles stabilized on their surface with at least one stabilizer, and are often referred to as “NADs” [non-aqueous dispersions],
aqueous dispersions of particles of film-forming polymers, which are often known as “latices”; in this case, the composition should comprise an aqueous phase besides the organic liquid medium,
water-soluble film-forming polymers; in this case, the composition should comprise an aqueous phase besides the organic liquid medium.
In one embodiment, the film former is a film-forming organic polymer which is soluble in the organic liquid medium.
I/ Polymers that are Soluble in the Organic Liquid Medium
When the organic liquid medium of the composition comprises at least one oil, the film former may be a polymer that is soluble in the the said oil. In this case, it is referred to as a fat-soluble polymer. The fat-soluble polymer may be of any chemical type and may especially be selected from:
a) fat-soluble, amorphous homopolymers and copolymers of olefins, of cycloolefins, of butadiene, of isoprene, of styrene, of vinyl ethers, esters or amides, or of (meth)acrylic acid esters or amides comprising a linear, branched or cyclic C₄-C₅₀alkyl group, which are preferably amorphous. The preferred fat-soluble homopolymers and copolymers are obtained from monomers selected from the group consisting of isooctyl(meth)acrylate, isononyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, lauryl(meth)acrylate, isopentyl(meth)acrylate, n-butyl(meth)acrylate, isobutyl(meth)acrylate, methyl(meth)acrylate, tert-butyl(meth)acrylate, tridecyl(meth)acrylate and stearyl(meth)acrylate, or mixtures thereof. Examples that will be mentioned include the alkyl acrylate/cycloalkyl acrylate copolymer sold by Phoenix Chem. under the name Giovarez AC-5099 ML, and vinylpyrrolidone copolymers, such as copolymers of a C₂to C₃₀alkene, such as a C₃to C₂₂alkene, and combinations thereof, may be used. As examples of VP copolymers that may be used in the invention, mention may be made of copolymers of VP/vinyl laurate, VP/vinyl stearate, butylated polyvinylpyrrolidone (PVP), VP/hexadecene, VP/triacontene or VP/acrylic acid/lauryl methacrylate.
Particular fat-soluble copolymers that may be mentioned include:
i) silicone-acrylic graft polymers having a silicone skeleton and acrylic grafts or having an acrylic skeleton and silicone grafts, such as the product sold under the name SA 70.5 by 3M and described in patents U.S. Pat. No. 5,725,882, U.S. Pat. No. 5,209,924, U.S. Pat. No. 4,972,037, U.S. Pat. No. 4,981,903, U.S. Pat. No. 4,981,902 and U.S. Pat. No. 5,468,477, and in patents U.S. Pat. No. 5,219,560 and EP 0 388 582;
ii) fat-soluble polymers belonging to one of the classes described above and bearing fluoro groups, in particular those described in patent U.S. Pat. No. 5,948,393 and the alkyl(meth)acrylate/perfluoroalkyl(meth)acrylate copolymers described in patents EP 0 815 836 and U.S. Pat. No. 5,849,318;
iii) polymers or copolymers resulting from the polymerization or copolymerization of an ethylenic monomer comprising one or more ethylenic, preferably conjugated, bonds (or dienes). As polymers or copolymers resulting from the polymerization or copolymerization of an ethylenic monomer, it is possible to use vinyl, acrylic or methacrylic copolymers.
In one embodiment, the film former is a block copolymer comprising at least one block composed of styrene units or styrene derivatives (for example methylstyrene, chlorostyrene or chloromethylstyrene). The copolymer comprising at least one styrene block may be a diblock or triblock copolymer, or even a multiblock copolymer, in starburst or radial form. The copolymer comprising at least one styrene block may also comprise, for example, an alkylstyrene (AS) block, an ethylene/butylene (EB) block, an ethylene/propylene (EP) block, a butadiene (B) block, an isoprene (I) block, an acrylate (A) block, a methacrylate (MA) block or a combination of these blocks. The copolymer comprising at least one block composed of styrene units or styrene derivatives may be a triblock copolymer, and in particular of the polystyrene/polyisoprene or polystyrene/polybutadiene type, such as those sold or manufactured under the name “Luvitol HSB” by BASF, and those of the polystyrene/copoly(ethylene-propylene) type or alternatively of the polystyrene/copoly(ethylene-butylene) type, such as those sold or manufactured under the brand name “Kraton” by Shell Chemical Co. or Gelled Permethyl 99A by Penreco may be used. Styrene-methacrylate copolymers may also be used.
Copolymer comprising at least one block composed of styrene or styrene-derived units may be, for example, Kraton G1650 (SEBS), Kraton G1651 (SEBS), Kraton G1652 (SEBS), Kraton G1657X (SEBS), Kraton G1701X (SEP), Kraton G1702X (SEP), Kraton G1726X (SEB), Kraton D-1101 (SBS), Kraton D-1102 (SBS), Kraton D-1107 (SIS), Gelled Permethyl 99A-750, Gelled Permethyl 99A-753-58 (blend of triblock polymer and of starburst block polymer), Gelled Permethyl 99A-753-59 (blend of triblock polymer and of starburst block polymer), Versagel 5970 and Versagel 5960 from Penreco (blend of triblock polymer and of starburst polymer in isododecane), and OS 129880, OS 129881 and OS 84383 from Lubrizol (styrene-methacrylate copolymer).
In one embodiment, the film former is selected from copolymers of a vinyl ester (the vinyl group being directly attached to the oxygen atom of the ester group and the vinyl ester having a saturated, linear or branched hydrocarbon-based radical of 1 to 19 carbon atoms, linked to the carbonyl of the ester group) and of at least one other monomer, which may be a vinyl ester (other than the vinyl ester already present), an α-olefin (containing from 8 to 28 carbon atoms), an alkyl vinyl ether (the alkyl group of which contains from 2 to 18 carbon atoms) or an allylic or methallylic ester (containing a saturated, linear or branched hydrocarbon-based radical of 1 to 19 carbon atoms, linked to the carbonyl of the ester group).
These copolymers may be partially crosslinked using crosslinking agents, which may be either of the vinyl type or of the allylic or methallylic type, such as tetraallyloxyethane, divinylbenzene, divinyl octanedioate, divinyl dodecanedioate, and divinyl octadecanedioate.
Examples of these copolymers that may be mentioned include the following copolymers: vinyl acetate/allyl stearate, vinyl acetate/vinyl laurate, vinyl acetate/vinyl stearate, vinyl acetate/octadecene, vinyl acetate/octadecyl vinyl ether, vinyl propionate/allyl laurate, vinyl propionate/vinyl laurate, vinyl stearate/1-octadecene, vinyl acetate/1-dodecene, vinyl stearate/ethyl vinyl ether, vinyl propionate/cetyl vinyl ether, vinyl stearate/allyl acetate, vinyl 2,2-dimethyloctanoate/vinyl laurate, allyl 2,2-di-methylpentanoate/vinyl laurate, vinyl dimethyl-propionate/vinyl stearate, allyl dimethylpropionate/vinyl stearate, vinyl propionate/vinyl stearate, crosslinked with 0.2% divinylbenzene, vinyl dimethyl-propionate/vinyl laurate, crosslinked with 0.2% divinylbenzene, vinyl acetate/octadecyl vinyl ether, crosslinked with 0.2% tetraallyloxyethane, vinyl acetate/allyl stearate, crosslinked with 0.2% divinyl-benzene, vinyl acetate/1-octadecene, crosslinked with 0.2% divinylbenzene, and allyl propionate/allyl stearate, crosslinked with 0.2% divinylbenzene.
Fat-soluble film-forming polymers that may also be mentioned include fat-soluble copolymers, and in particular those resulting from the copolymerization of vinyl esters containing from 9 to 22 carbon atoms or of alkyl acrylates or methacrylates, the alkyl radicals containing from 10 to 20 carbon atoms.
Such fat-soluble copolymers may be selected from copolymers of polyvinyl stearate, polyvinyl stearate crosslinked with divinylbenzene, with diallyl ether or with diallyl phthalate, polystearyl (meth)acrylate, polyvinyl laurate and polylauryl (meth)acrylate copolymers, these poly(meth)acrylates possibly being crosslinked with ethylene glycol dimethacrylate or tetraethylene glycol dimethacrylate.
The fat-soluble copolymers defined above are known and described especially in patent application FR-A-2 232 303; they may have a weight-average molecular weight ranging from 2000 to 500 000 and preferably from 4000 to 200 000.
As examples of fat-soluble polymers that may be used in the invention, mention may be made of poly-alkylenes and C₂-C₂₀alkene copolymers, in particular polybutene.
b) amorphous and fat-soluble polycondensates, preferably not comprising any groups donating hydrogen interactions, in particular aliphatic polyesters having C_4-50alkyl side chains or else polyesters resulting from the condensation of fatty acid dimers, or even polyesters comprising a silicone-based segment in the form of a block, graft or end group, which are solid at ambient temperature, as defined in patent application FR 0 113 920, not yet published.
c) amorphous and fat-soluble polysaccharides comprising alkyl (ether or ester) side chains, in particular alkylcelluloses containing a saturated or unsaturated, linear or branched C₁to C₈alkyl radical, such as ethylcellulose and propylcellulose.
The film-forming polymer may be selected in particular from cellulose-based polymers such as nitro-cellulose, cellulose acetate, cellulose acetobutyrate, cellulose acetopropionate or ethylcellulose, or else from polyurethanes, acrylic polymers, vinyl polymers, polyvinyl butyrals, alkyd resins, resins derived from aldehyde condensation products, such as aryl-sulphonamide-formaldehyde resins, for instance toluenesulphonamide-formaldehyde resin, and aryl-sulphonamide epoxy resins.
Film-forming polymers that may especially be used include nitrocellulose RS ⅛ sec.; RS ¼ sec.; ½ sec.; RS 5 sec.; RS 15 sec.; RS 35 sec.; RS 75 sec.; RS 150 sec.; AS ¼ sec.; AS ½ sec.; SS ¼ sec.; SS ½ sec.; SS 5 sec., sold especially by the company Hercules; the toluenesulphonamide-formaldehyde resins “Ketjentflex MS80” from the company Akzo or “Santolite MHP” and “Santolite MS80” from the company Faconnier or “Resimpol 80” from the company Pan Americana, the alkyd resin “Beckosol Ode 230-70-E” from the company Dainippon, the acrylic resin “Acryloid B66” from the company-Rohm & Haas, and the polyurethane resin “Trixene PR 4127” from the company Baxenden.
d) silicone resins which are soluble or swellable by silicone oils. These resins are partially crosslinked polyorganosiloxanes which, depending on the degree of crosslinking, will be soluble or swellable by the silicone oils of the oily phase of the organic liquid medium. These silicone resins may be selected from the following non-limitative list: MQ resins or trimethylsiloxysilicates, polysilsesquioxanes or crosslinked dimethicone/vinyldimethicone polymers.
II/ Non-Aqueous Dispersions of Polymer Particles
The composition may contain a film former selected from non-aqueous dispersions of polymer particles. The particles are generally spherical. Before being incorporated into the composition of the invention, the particles are generally dispersed in a physiologically acceptable liquid fatty phase, such as hydrocarbon-based oils or silicone oils. According to one mode of implementation, these dispersions are generally known as NADs (non-aqueous dispersions) of polymer, as opposed to networks, which are aqueous dispersions of polymer. These dispersions may especially be in the form of nanoparticles of polymers in stable dispersion in the said fatty phase. In one embodiment the nanoparticles are between 5 nm and 600 nm in size. However, it is possible to obtain polymer particles ranging up to 1 μm in size.
One of the advantages of the polymer dispersion of the composition of the invention is the possibility of varying the glass transition temperature (Tg) of the polymer or the polymer system (polymer plus additive of the plasticizer type), and of thus going from a hard polymer to a more or less soft polymer, making it possible to adjust the mechanical properties of the composition depending on the intended application and in particular on the film deposited.
The polymers in dispersion which may be used in the composition of the invention preferably have a molecular weight ranging from about 2000 to 10 000 000 and a Tg ranging from −100° C. to 300° C. and better still from '150° C. to 50° C. and preferably from −10° C. to 100° C.
It is possible to use film-forming polymers, that preferably have a low Tg, of less than or equal to the temperature of the skin and especially less than or equal to 40° C. A dispersion is thus obtained which can form a film when it is applied to a support.
Among the film-forming polymers which may be mentioned are free-radical, acrylic or vinyl homo-polymers or copolymers, preferably having a Tg of less than or equal to 40° C. and especially ranging from −10° C. to 30° C., used alone or as a mixture.
The expression “free-radical polymer” means a polymer obtained by polymerization of monomers containing unsaturation, especially ethylenic unsaturation, each monomer being capable of homo-polymerizing (unlike polycondensates). The free-radical polymers may especially be vinyl polymers or copolymers, especially acrylic polymers.
The vinyl polymers may result from the polymerization of ethylenically unsaturated monomers containing at least one acid group and/or esters of these acidic monomers and/or amides of these acids.
As monomers bearing an acidic group, it is possible to use α,β-ethylenic unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid or itaconic acid. (Meth)acrylic acid and crotonic acid are preferably used, and more preferentially (meth)acrylic acid.
The esters of acidic monomers are advantageously selected from the esters of (meth)acrylic acid (also known as (meth)acrylates), for instance alkyl (meth)acrylates, in particular of a C₁-C₂₀and preferably a C₁-C₆alkyl, aryl (meth)acrylates, in particular of a C₆-C₁₀aryl, and hydroxyalkyl (meth)acrylates, in particular of a C₂-C₆hydroxyalkyl. Alkyl (meth)acrylates which may be mentioned include methyl, ethyl, butyl, isobutyl, 2-ethylhexyl and lauryl (meth)acrylate. Hydroxyalkyl (meth)acrylates which may be mentioned include hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate. Aryl (meth)acrylates which may be mentioned include benzyl or phenyl acrylate.
The (meth)acrylic acid esters that are particularly preferred are alkyl (meth)acrylates.
The free-radical polymers that are preferably used are copolymers of (meth)acrylic acid and of an alkyl (meth)acrylate, especially of a C₁-C₄alkyl. More preferentially, methyl acrylates may be used, optionally copolymerized with acrylic acid.
The amides of the acidic monomers which may be mentioned include (meth)acrylamides, and especially N-alkyl(meth)acrylamides, in particular of a C₂-C₁₂alkyl, such as N-ethylacrylamide, N-t-butylacrylamide and N-octylacrylamide; N-di(C₁-C₄) alkyl(meth)acryl-amides.
The vinyl film-forming polymers can result from the polymerization of monomers containing ethylenic unsaturation and containing at least one acidic group and/or esters of these acidic monomers and/or amides of these acidic monomers.
Monomers bearing an acidic group which may be used are α,β-ethylenic unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid or itaconic acid. (Meth)acrylic acid and crotonic acid are preferably used, and more preferably (meth)acrylic acid.
The esters of acidic monomers are advantageously selected from (meth)acrylic acid esters (also known as (meth)acrylates), especially (meth)acrylates of an alkyl, in particular of a C₁-C₃₀and preferably a C₁-C₂₀alkyl, (meth)acrylates of an aryl, in particular of a C₆-C₁₀aryl, and (meth)acrylates of a hydroxyalkyl, in particular of a C₂-C₆hydroxyalkyl.
Among the alkyl (meth)acrylates that may be mentioned are methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate and cyclohexyl methacrylate.
Among the hydroxyalkyl(meth)acrylates that may be mentioned are hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate.
Among the aryl (meth)acrylates that may be mentioned are benzyl acrylate and phenyl acrylate.
The (meth)acrylic acid esters that are particularly preferred are the alkyl (meth)acrylates.
According to the present invention, the alkyl group of the esters may be either fluorinated or perfluorinated, i.e. some or all of the hydrogen atoms of the alkyl group are substituted by fluorine atoms.
Examples of amides of the acidic monomers that may be mentioned are (meth)acrylamides, and especially N-alkyl(meth)acrylamides, in particular of a C₂-C₁₂alkyl. Among the N-alkyl(meth)acrylamides that may be mentioned are N-ethylacrylamide, N-t-butylacrylamide, N-t-octylacrylamide and N-undecylacrylamide.
The vinyl film-forming polymers may also result from the homopolymerization or copolymerization of monomers selected from vinyl esters and styrenic monomers. In particular, these monomers may be polymerized with acidic monomers and/or esters thereof and/or amides thereof, such as those mentioned above.
Examples of vinyl esters that may be mentioned are vinyl acetate, vinyl neodecanoate, vinyl pivalate, vinyl benzoate and vinyl t-butylbenzoate.
Styrenic monomers that may be mentioned are styrene and alpha-methylstyrene.
In a non-limitative manner, the polymers in dispersion of the invention may be selected from the following polymers or copolymers: polyurethanes, polyurethane-acrylics, polyureas, polyurea-polyurethanes, polyester-polyurethanes, polyether-polyurethanes, polyesters, polyesteramides, fatty-chain polyesters, alkyds; acrylic and/or vinyl polymers or copolymers; acrylic-silicone copolymers; polyacrylamides; silicone polymers, for example silicone polyurethanes or silicone acrylics, and fluoro polymers, and mixtures thereof.
The polymer(s) in oily dispersion may represent (as solids or active substance) from 0.1% to 60%, preferably from 2% to 40% and better still from 4% to 25% of the weight of the composition. For a stabilizer that is solid at ambient temperature, the amount of solids in the dispersion represents the total amount of polymer and of stabilizer.
The fat-soluble or dispersible polymers in the composition of the invention may also be used in an amount ranging from 0.01% to 20% (as active substance), for instance from 1% to 10%, where appropriate, relative to the total weight of the composition.
III/ Aqueous Dispersions of Polymer Particles
According to another embodiment, the film-forming polymer may be selected from aqueous dispersions of polymer particles, in the case where the composition according to the invention comprises an aqueous phase.
The aqueous dispersion comprising one or more film-forming polymers may be prepared by a person skilled in the art on the basis of his or her general knowledge, especially by emulsion polymerization or by dispersion of the preformed polymer.
Among the film-forming polymers which may be used in the composition according to the present invention, mention may be made of synthetic polymers, of polycondensate type or of free-radical type, polymers of natural origin, and mixtures thereof.
Among the polycondensates, mention may thus be made of anionic, cationic, nonionic or amphoteric polyurethanes, polyurethane-acrylics, polyurethane-poly-vinylpyrrolidones, polyester-polyurethanes, polyether-polyurethanes, polyureas, polyurea-polyurethanes, and mixtures thereof.
The polyurethanes may be, for example, an aliphatic, cycloaliphatic or aromatic polyurethane, polyurea/polyurethane or polyurea copolymer, containing, alone or as a mixture,
at least one block of linear or branched aliphatic and/or cycloaliphatic and/or aromatic polyester origin, and/or
at least one block of aliphatic and/or cycloaliphatic and/or aromatic polyether origin, and/or
at least one substituted or unsubstituted, branched or unbranched silicone block, for example polydimethylsiloxane or polymethylphenylsiloxane, and/or
at least one block comprising fluoro groups.
The polyurethanes as defined in the invention may also be obtained from branched or unbranched polyesters or from alkyds containing mobile hydrogens, which are modified by means of a polyaddition with a diisocyanate and a difunctional organic co-reactive compound (for example dihydro, diamino or hydroxyamino), also containing either a carboxylic acid or carboxylate group, or a sulphonic acid or sulphonate group, or alternatively a neutralizable tertiary amine group or a quaternary ammonium group.
Mention may also be made of polyesters, polyesteramides, fatty-chain polyesters, polyamides and epoxy ester resins.
The polyesters may be obtained, in a known manner, by polycondensation of aliphatic or aromatic diacids with aliphatic or aromatic diols or with polyols. Succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid or sebacic acid may be used as aliphatic diacids. Terephthalic acid or isophthalic acid, or alternatively a derivative such as phthalic anhydride, may be used as aromatic diacids. Ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol, cyclohexanedimethanol and 4,4-N-(1-methylpropylidene)bisphenol may be used as aliphatic diols. Glycerol, pentaerythritol, sorbitol and trimethylolpropane may be used as polyols.
The polyesteramides may be obtained in a similar manner to the polyesters, by polycondensation of diacids with diamines or amino alcohols. Ethylenediamine, hexamethylenediamine or meta- or para-phenylenediamine may be used as diamine. Monoethanolamine may be used as amino alcohol.
As monomer bearing an anionic group which may be used during the polycondensation, mention may be made, for example, of dimethylolpropionic acid, trimellitic acid or a derivative such as trimellitic anhydride, the sodium salt of pentanediol-3-sulphonic acid and the sodium salt of 5-sulpho-1,3-benzenedicarboxylic acid. The fatty-chain polyesters may be obtained using fatty-chain diols during the polycondensation. The epoxy ester resins may be obtained by polycondensation of fatty acids with a condensate having α,ω-diepoxy ends.
The free-radical polymers may in particular be acrylic and/or vinyl polymers or copolymers. Anionic radical polymers are preferred. As a monomer bearing an anionic group which may be used during the free-radical polymerization, mention may be made of acrylic acid, methacrylic acid, crotonic acid, maleic anhydride or 2-acrylamido-2-methylpropanesulphonic acid.
The acrylic polymers may result from the copolymerization of monomers selected from the esters and/or amides of acrylic acid or of methacrylic acid. As examples of monomers of ester type, mention may be made of methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate and lauryl methacrylate. As examples of monomers of amide type, mention may be made of N-t-butylacrylamide and N-t-octylacrylamide.
Acrylic polymers obtained by copolymerization of ethylenically unsaturated monomers containing hydrophilic groups, preferably of nonionic nature, such as hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate, are preferably used.
The vinyl polymers may result from the homopolymerization or copolymerization of monomers selected from vinyl esters, styrene or butadiene. As examples of vinyl esters, mention may be made of vinyl acetate, vinyl neodecanoate, vinyl pivalate, vinyl benzoate and vinyl t-butylbenzoate.
Acrylic/silicone copolymers or even nitrocellulose/acrylic copolymers may also be used.
The polymers of natural origin, which are optionally modified, may be selected from shellac, sandarac gum, dammar resins, elemi gums, copal resins, cellulose derivatives, and mixtures thereof.
Mention may also be made of the polymers resulting from the free-radical polymerization of one or more free-radical monomers inside and/or partially at the surface of preexisting particles of at least one polymer selected from the group consisting of polyurethanes, polyureas, polyesters, polyesteramides and/or alkyds. These polymers are generally referred to as “hybrid polymers”.
When an aqueous dispersion of polymer particles is used, the solids content of the the said aqueous dispersion may be from about 5% to 60% and preferably from 30% to 50% by weight.
The size of the polymer particles in aqueous dispersion may be between 10 and 500 nm and is preferably between 20 and 150 nm, allowing the production of a film of noteworthy gloss. However, particle sizes ranging up to 1 micron may be used.
Aqueous dispersions of film-forming polymers that may be used include the acrylic dispersions sold under the names Neocryl XK-90®, Neocryl A-1070®, Neocryl A-1090®, Neocryl BT-62®, Neocryl A-1079® and Neocryl A-523® by the company Avecia-Neoresins, Dow Latex 432® by the company Dow Chemical, Daitosol 5000 AD® or Daitosol 5000 SJ by the company Daito Kasey Kogyo; Syntran 5760 by the company Interpolymer or the aqueous dispersions of polyurethane sold under the names Neorez R-981® and Neorez R-974® by the company Avecia-Neoresins, Avalure UR-405®, Avalure UR-410®, Avalure UR-425®, Avalure UR-450®, Sancure 875®, Sancure 861®, Sancure 878® and Sancure 2060® by the company Goodrich, Impranil 85® by the company Bayer and Aquamere H-1511® by the company Hydromer; the sulphopolyesters sold under the brand name Eastman AQ® by the company Eastman Chemical Products, and vinyl dispersions, for instance Mexomere PAM.
IV/ Water-Soluble Polymers
In the case where the composition comprises an aqueous phase, the film-forming polymer may be a water-soluble polymer. The water-soluble polymer is thus dissolved in the aqueous phase of the composition.
Among the water-soluble film-forming polymers that may be mentioned are the following cationic polymers:
(1) acrylic polymers or copolymers, such as polyacrylates or polymethacrylates; the copolymers of the family (1) may also contain one or more units derived from comonomers that may be selected from the family of acrylamides, methacrylamides, diacetone-acrylamides, acrylamides and methacrylamides substituted on the nitrogen by lower alkyls, acrylic or methacrylic acids or esters thereof, vinyllactams such as vinylpyrrolidone or vinylcaprolactam, or vinyl esters.
Thus, among these copolymers of the family (1), mention may be made of:
copolymers of acrylamide and of dimethylaminoethyl methacrylate, quaternized with dimethyl sulphate or with a dimethyl halide, such as the product sold under the name Hercofloc by the company Hercules,
the copolymer of acrylamide and of methacryloyloxyethyltrimethylammonium chloride described, for example, in patent application EP-A-080 976 and sold under the name Bina Quat P 100 by the company Ciba Geigy,
the copolymer of acrylamide and of methacryloyloxyethyltrimethylammonium methosulphate sold under the name Reten by the company Hercules,
quaternized or non-quaternized copolymers of vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate, such as the products sold under the name “Gafquat” by the company ISP, for instance “Gafquat 734” or “Gafquat 755”, or alternatively the products denoted as “Copolymer 845, 958 and 937”. These polymers are described in detail in French patents 2 077 143 and 2 393 573,
terpolymers of dimethylaminoethyl methacrylate/vinylcaprolactam/vinylpyrrolidone, such as the product sold under the name Gaffix VC 713 by the company ISP; and
the quaternized copolymer of vinyl-pyrrolidone/dimethylaminopropylmethacrylamide, such as the product sold under the name “Gafquat HS 100” by the company ISP;
(2) the quaternized polysaccharides described more particularly in patents U.S. Pat. No. 3,589,578 and U.S. Pat. No. 4,031,307, such as guar gums containing trialkyl-ammonium cationic groups. Such products are sold in particular under the trade names Jaguar C13 S, Jaguar C 15 and Jaguar C 17 by the company Meyhall;
(3) quaternary copolymers of vinylpyrrolidone and of vinylimidazole;
(4) chitosans or salts thereof;
(5) cationic cellulose derivatives such as copolymers of cellulose or of cellulose derivatives grafted with a water-soluble monomer comprising a quaternary ammonium, and described in particular in patent U.S. Pat. No. 4,131,576, such as hydroxyalkylcelluloses, for instance hydroxymethyl-, hydroxyethyl- or hydroxy-propylcelluloses grafted in particular with a methacryloyloxyethyltrimethylammonium, methacrylamidopropyltrimethylammonium or dimethyldiallylammonium salt. The products sold corresponding to this definition are, more particularly, the products sold under the name “Celquat L 200” and “Celquat H 100” by the National Starch Company.
Among the film-forming water-soluble polymers that may be mentioned are the following amphoteric polymers:
(1) polymers resulting from the copolymerization of a monomer derived from a vinyl compound bearing a carboxylic group such as, more particularly, acrylic acid, methacrylic acid, maleic acid, α-chloroacrylic acid, and a basic monomer derived from a substituted vinyl compound containing at least one basic atom, such as, more particularly, dialkylaminoalkyl methacrylate and acrylate, dialkylaminoalkylmethacrylamide and -acrylamide. Such compounds are described in patent U.S. Pat. No. 3,836,537;
(2) polymers comprising units derived from:
a) at least one monomer selected from acrylamides and methacrylamides substituted on the nitrogen with an alkyl radical,
b) at least one acidic comonomer containing one or more reactive carboxylic groups, and
c) at least one basic comonomer such as esters containing primary, secondary, tertiary and quaternary amine substituents of acrylic and methacrylic acids, and the product of quaternization of dimethylaminoethyl methacrylate with dimethyl or diethyl sulphate;
(3) crosslinked alkylpolyaminoamides totally or partially derived from polyaminoamides;
(4) polymers comprising zwitterionic units;
(5) chitosan-derived polymer;
(6) polymers derived from the N-carboxy-alkylation of chitosan, such as N-carboxymethylchitosan or N-carboxybutylchitosan sold under the name “Evalsan” by the company Jan Dekker;
(7) (C₁-C₅)alkyl vinyl ether/maleic anhydride copolymers, partially modified by a semi-amidation with an N,N-dialkylaminoalkylamine, such as N,N-dimethyl-aminopropylamine, or by a semi-esterification with an N,N-dialkanolamine. These copolymers may also comprise other vinyl comonomers, such as vinylcaprolactam.
The water-soluble film-forming polymers are preferably selected from the group consisting of:
proteins, for instance proteins of plant origin, such as wheat proteins and soya proteins; proteins of animal origin, such as keratin, for example keratin hydrolysates and sulphonic keratins;
anionic, cationic, amphoteric or nonionic chitin or chitosan polymers;
cellulosic polymers, such as hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, ethylhydroxyethylcellulose and carboxymethylcellulose, and quaternized cellulose derivatives;
acrylic polymers or copolymers, such as polyacrylates or polymethacrylates;
vinyl polymers, for instance polyvinylpyrrolidones, copolymers of methyl vinyl ether and of maleic anhydride, the copolymer of vinyl acetate and of crotonic acid, copolymers of vinylpyrrolidone and of vinyl acetate;
copolymers of vinylpyrrolidone and of caprolactam; polyvinyl alcohols;
polymers of natural origin, which are optionally modified, such as:
gum arabic, guar gum, xanthan derivatives, karaya gum;
alginates and carrageenans;
glycosaminoglycans, hyaluronic acid and derivatives thereof;
shellac, sandarac gum, dammar resins, elemi gums and copal resins;
deoxyribonucleic acid;
mucopolysaccharides such as hyaluronic acid and chondroitin sulphate, and mixtures thereof.
These polymers will be used in particular if a more or less appreciable removal of the film by water is desired.
In order to improve the film-forming nature of an oily or aqueous polymer, it is possible to add to the polymer system a coalescer, which will be selected from the known coalescers.
According to one embodiment of the invention, the film-forming polymer may be selected from polymers containing a non-silicone organic skeleton grafted with monomers containing a polysiloxane. These polymers may be fat-soluble, lipodispersible, water-soluble or dispersible in aqueous medium, where appropriate.
The polymers containing a non-silicone organic skeleton grafted with monomers containing a polysiloxane consist of an organic main chain formed from organic monomers not comprising silicone, onto which is grafted, within the said chain and also optionally on at least one of its ends, at least one polysiloxane macromer.
In the text hereinbelow, in accordance with what is generally accepted, the expression “polysiloxane macromer” is understood to refer to any monomer containing a polysiloxane-type polymer chain in its structure.
The non-silicone organic monomers constituting the main chain of the grafted silicone polymer can be selected from free-radically polymerizable monomers containing ethylenic unsaturation, polycondensation-polymerizable monomers, such as those forming polyamides, polyesters or polyurethanes, and ring-opening monomers, such as those of the oxazoline or caprolactone type.
The polymers containing a non-silicone organic skeleton grafted with monomers containing a polysiloxane, in accordance with the present invention, can be obtained according to any means known to those skilled in the art, in particular by reaction between (i) a starting polysiloxane macromer which is correctly functionalized on the polysiloxane chain and (ii) one or more non-silicone organic compounds, themselves correctly functionalized with a function which is capable of reacting with the functional group(s) borne by the said silicone, forming a covalent bond; a classic example of such a reaction is the free-radical reaction between a vinyl group borne on one of the ends of the silicone with a double bond of a monomer containing ethylenic unsaturation in the main chain.
The polymers containing a non-silicone organic skeleton grafted with monomers containing a polysiloxane, in accordance with the invention, are more preferably selected from those described in patents U.S. Pat. No. 4,693,935, U.S. Pat. No. 4,728,571 and U.S. Pat. No. 4,972,037 and patent applications EP-A-0 412 704, EP-A-0 412 707, EP-A-0 640 105 and WO 95/00578. These are copolymers obtained by free-radical polymerization starting with monomers containing ethylenic unsaturation and monomers having a terminal vinyl group, or alternatively copolymers obtained by reaction of a polyolefin comprising functionalized groups and a polysiloxane macromer having a terminal function which is reactive with the said functionalized groups.
One particular family of grafted silicone polymers which is suitable for carrying out the present invention consists of grafted silicone polymers comprising:
a) from 0% to 98% by weight of at least one free-radically polymerizable lipophilic monomer (A) of low polarity containing ethylenic unsaturation;
b) from 0% to 98% by weight of at least one polar hydrophilic monomer (B) containing ethylenic unsaturation, which is copolymerizable with the monomer(s) of the type (A);
c) from 0.01% to 50% by weight of at least one polysiloxane macromer (C) of general formula:
X(Y)_nSi(R)_3-mZ_m (I)
in which:

- X denotes a vinyl group which is copolymerizable with the monomers (A) and (B);
- Y denotes a divalent bonding group;
- R denotes hydrogen, C₁-C₆alkyl or alkoxy, or C₆-C₁₂aryl;
- Z denotes a monovalent polysiloxane unit with a number-average molecular weight of at least 500;
- n is 0 or 1 and m is an integer ranging from 1 to 3;
- the percentages being calculated relative to the total weight of the monomers (A), (B) and (C).

These polymers have a number-average molecular weight ranging from 10 000 to 2 000 000 and preferably a glass transition temperature Tg or a crystalline melting temperature Tm of at least −20° C.
As examples of lipophilic monomers (A), mention may be made of acrylic or methacrylic acid esters of C₁-C₁₈alcohols; methacrylic acid esters of C₁₂-C₃₀alcohols, styrene; polystyrene macromers; vinyl acetate; vinyl propionate; alpha-methylstyrene; tert-butylstyrene; butadiene; cyclohexadiene; ethylene; propylene; vinyltoluene; acrylic or methacrylic acid esters of 1,1-dihydroperfluoroalkanols or of homologues thereof; acrylic or methacrylic acid esters of omega-hydrofluoroalkanols; acrylic or methacrylic acid esters of fluoroalkylsulphonamido alcohols; acrylic or methacrylic acid esters of fluoroalkyl alcohols; acrylic or methacrylic acid esters of fluoroether alcohols; or mixtures thereof. The preferred monomers (A) are selected from the group consisting of n-butyl methacrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, methyl methacrylate, 2-(N-methylperfluorooctanesulphonamido)ethyl acrylate and 2-(N-butylperfluorooctanesulphonamido)ethyl acrylate, and mixtures thereof.
As examples of polar monomers (B), mention may be made of acrylic acid, methacrylic acid, N,N-dimethylacrylamide, dimethylaminoethyl methacrylate, quaternized dimethylaminoethyl methacrylate, (meth)acrylamide, N-t-butylacrylamide, maleic acid, maleic anhydride and hemiesters thereof, hydroxyalkyl (meth)acrylates, diallyldimethylammonium chloride, vinylpyrrolidone, vinyl ethers, maleimides, vinylpyridine, vinylimidazole, heterocyclic vinyl polar compounds, styrene sulphonate, allyl alcohol, vinyl alcohol and vinylcaprolactam, or mixtures thereof. The preferred monomers (B) are selected from the group consisting of acrylic acid, N,N-dimethylacrylamide, dimethylaminoethyl methacrylate, quaternized dimethylaminoethyl methacrylate and vinylpyrrolidone, and mixtures thereof.
Mention is made especially of the product KP 561 or KP 562 sold by Shin Etsu such that the monomer (A) is selected from esters of a C₁₈-C₂₂alcohol and of methacrylic acid.
The polysiloxane macromers (C) of formula (I) are selected preferably from those corresponding to the general formula (II) below:

in which:

- R¹is hydrogen or —COOH (preferably hydrogen);
- R²is hydrogen, methyl or —CH₂COOH (preferably methyl);
- R³is C₁-C₆alkyl, alkoxy or alkylamino, C₆-C₁₂aryl or hydroxyl (preferably methyl);
- R⁴is C₁-C₆alkyl, alkoxy or alkylamino, C₆-C₁₂aryl or hydroxyl (preferably methyl);
- q is an integer from 2 to 6 (preferably 3);
- p is 0 or 1;
- r is an integer from 5 to 700;
- m is an integer from 1 to 3 (preferably 1).

Preference is given to using the polysiloxane macromers of formula:

with n being a number ranging from 5 to 700 and 1 being an integer between 0 and 3.
One embodiment of the invention consists in using a copolymer which may be obtained by free-radical polymerization starting from the monomer mixture consisting of:

- a) 60% by weight of tert-butyl acrylate;
- b) 20% by weight of acrylic acid;
- c) 20% by weight of silicone macromer of formula:
  
  with n being a number ranging from 5 to 700 and 1 being an integer between 0 and 3, the weight percentages being calculated relative to the total weight of the monomers.

Another particular embodiment of the invention consists in using a copolymer which may be obtained by free-radical polymerization starting from the monomer mixture consisting of:

- a) 80% by weight of tert-butyl acrylate;
- b) 20% by weight of silicone macromer of formula:
  
  with n being a number ranging from 5 to 700 and 1 being an integer between 0 and 3, the weight percentages being calculated relative to the total weight of the monomers.

Another particular family of grafted silicone polymers containing a non-silicone organic skeleton that is suitable for carrying out the present invention consists of grafted silicone copolymers which may be obtained by reactive extrusion-moulding of a polysiloxane macromer with a reactive terminal function on a polymer of the polyolefin type comprising reactive groups capable of reacting with the terminal function of the polysiloxane macromer to form a covalent bond for grafting the silicone onto the main chain of the polyolefin. These polymers are described, along with a process for their preparation, in patent application WO 95/00578.
The reactive polyolefins are preferably selected from polyethylenes and polymers of ethylene-derived monomers such as propylene, styrene, alkyl-styrene, butylene, butadiene, (meth)acrylates, vinyl esters or equivalents, comprising reactive functions capable of reacting with the terminal function of the polysiloxane macromer. They are selected more particularly from copolymers of ethylene or of ethylene derivatives and of monomers selected from those comprising a carboxylic function such as (meth)acrylic acid; those comprising an acid anhydride function such as maleic anhydride; those comprising an acid chloride function such as (meth)acryloyl chloride; those comprising an ester function such as (meth)acrylic acid esters; those comprising an isocyanate function.
The silicone macromers are preferably selected from polysiloxanes comprising a functionalized group, at the end of the polysiloxane chain or close to the end of the said chain, selected from the group consisting of alcohols, thiols, epoxy groups and primary and secondary amines, and more particularly from those corresponding to the general formula:
T-(CH₂)₆—Si—[—(OSiR⁵R⁶)_t—R⁷]_y (III)
in which T is selected from the group consisting of NH₂, NHRN and an epoxy, OH, or SH function; R⁵, R⁶, R⁷and RN independently denote a C₁-C₆alkyl, phenyl, benzyl, or C₆-C₁₂alkylphenyl or hydrogen; s is a number from 2 to 100; t is a number from 0 to 1000 and y is a number from 1 to 3. They have a number-average molecular weight preferably ranging from 5000 to 300 000, more preferably from 8000 to 200 000 and more particularly from 9000 to 40 000.
According to one preferred embodiment, the film-forming polymer may be purchased from the Minnesota Mining and Manufacturing Company under the trade names of “Silicone Plus” polymers. For example, poly(isobutyl methacrylate-co-methyl FOSEA)-g-poly(dimethylsiloxane) is sold under the trade name SA 70-5 IBMMF.
According to another preferred form of the invention, the film-forming polymer is selected from silicone polymers grafted with non-silicone organic monomers. These polymers may be fat-soluble, fat-dispersible, water-soluble or dispersible in aqueous medium, where appropriate.
The said grafted silicone polymer(s) containing a polysiloxane skeleton grafted with non-silicone organic monomers comprise a silicone (or polysiloxane (/SiO—)_n) main chain onto which is grafted, within the said chain and also optionally on at least one of its ends, at least one organic group not comprising silicone.
The polymers containing a polysiloxane skeleton grafted with non-silicone organic monomers, according to the invention, can be existing commercial products or alternatively can be obtained according to any means known to those skilled in the art, in particular by reaction between (i) a starting silicone which is correctly functionalized on one or more of these silicon atoms, and (ii) a non-silicone organic compound which is itself correctly functionalized with a function which is capable of reacting with the functional group(s) borne by the said silicone, forming a covalent bond; a classic example of such a reaction is the hydrosilylation reaction between /Si—H groups and vinyl groups CH₂═CH—, or alternatively the reaction between thio functional groups —SH with these same vinyl groups.
Examples of polymers containing a poly-siloxane skeleton grafted with non-silicone organic monomers that are suitable for carrying out the present invention, and also their specific mode of preparation, are described in particular in patent applications EP-A-0 582 152, WO 93/23009 and WO 95/03776, the teachings of which are included in their entirety in the present description by way of non-limitative references.
According to a particularly preferred embodiment of the present invention, the silicone polymer containing a polysiloxane skeleton grafted with non-silicone organic monomers which is used comprises the result of a free-radical copolymerization between, on the one hand, at least one non-silicone anionic organic monomer containing ethylenic unsaturation and/or a non-silicone hydrophobic organic monomer containing ethylenic unsaturation, and, on the other hand, a silicone containing in its chain at least one, and preferably several, functional group(s) capable of reacting with the said ethylenic unsaturations of the said non-silicone monomers, forming a covalent bond, in particular thio functional groups.
According to the present invention, the said anionic monomers containing ethylenic unsaturation are preferably selected, alone or as mixtures, from linear or branched, unsaturated carboxylic acids, optionally partially or totally neutralized in the form of a salt, it being possible for this or these unsaturated carboxylic acid(s) to be, more particularly, acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid and crotonic acid. The suitable salts are, in particular, alkali metal salts, alkaline-earth metal salts and ammonium salts. It will likewise be noted that, in the final grafted silicone polymer, the organic group of anionic nature which comprises the result of the free-radical (homo)polymerization of at least one anionic monomer of unsaturated carboxylic acid type can, after reaction, be post-neutralized with a base (sodium hydroxide, aqueous ammonia, etc.) in order to turn it into a salt.
According to the present invention, the hydrophobic monomers containing ethylenic unsaturation are preferably selected, alone or as mixtures, from acrylic acid esters of alkanols and/or methacrylic acid esters of alkanols. The alkanols are preferably C₁-C₃₀and more particularly C₁-C₂₂. The preferred monomers are selected from the group consisting of isooctyl(meth)acrylate, isononyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, lauryl(meth)acrylate, isopentyl(meth)acrylate, n-butyl(meth)acrylate, isobutyl(meth)acrylate, methyl(meth)acrylate, tert-butyl(meth)acrylate, tridecyl(meth)acrylate and stearyl(meth)acrylate, or mixtures thereof.
One family of silicone polymers containing a polysiloxane skeleton grafted with non-silicone organic monomers that is particularly suitable for carrying out the present invention consists of silicone polymers comprising in their structure the unit of formula IV below:

in which the radicals G₁, which are identical or different, represent hydrogen, a C₁-C₁₀alkyl radical or a phenyl radical; the radicals G₂, which may be identical or different, represent a C₁-C₁₀alkylene group; G₃represents a polymer residue resulting from the (homo)polymerization of at least one anionic monomer containing ethylenic unsaturation; G₄represents a polymer residue resulting from the (homo)-polymerization of at least one hydrophobic monomer containing ethylenic unsaturation; m and n are equal to 0 or 1; a is an integer ranging from 0 to 50; b is an integer which may be between 10 and 350, c is an integer ranging from 0 to 50; with the proviso that one of the parameters a and c is other than 0.
Preferably, the unit of formula (IV) of the above text has at least one, and even more preferably all, of the following characteristics:
the radicals G₁denote an alkyl radical, preferably a methyl radical;
n is not zero, and the radicals G₂represent a divalent C₁-C₃radical, preferably a propylene radical;
G₃represents a polymer radical resulting from the (homo)polymerization of at least one monomer of the carboxylic acid type containing ethylenic unsaturation, preferably acrylic acid and/or methacrylic acid;
G₄represents a polymer radical resulting from the homo polymerization of at least one monomer of the C₁-C₁₀alkyl (meth)acrylate type, preferably isobutyl or methyl (meth)acrylate.
Examples of silicone polymers corresponding to the formula (IV) are, in particular, polydimethyl-siloxanes (PDMSs) onto which are grafted, via a thiopropylene-type connecting chain, mixed polymer units of the poly(meth)acrylic acid type and of the polyalkyl (meth)acrylate type.
Other examples of silicone polymers corresponding to formula (IV) are, in particular, polydimethylsiloxanes (PDMSs) onto which are grafted, via a thiopropylene-type connecting chain, polymer units of the polyisobutyl (meth)acrylate type.
Such polymers include polymers comprising at least one group of formula:

in which

- a, b and c, which may be identical or different, are each a number ranging from 1 to 100 000; and the end groups, which may be identical or different, are each selected from linear C₁-C₂₀alkyl groups, C₃-C₂₀branched-chain alkyl groups, C₃-C₂₀aryl groups, linear C₁-C₂₀alkoxy groups and branched C₃-C₂₀alkoxy groups.

Such polymers are disclosed in patents U.S. Pat. Nos. 4,972,037, 5,061,481, 5,209,924, 5,849,275, 6,033,650 and WO 93/23446 and WO 95/06078.
Another family of silicone polymers having a polysiloxane skeleton grafted with non-silicone organic monomers, which is particularly suitable for performing the present invention, consists of silicone polymers comprising in their structure the unit of formula (V) below:

in which the radicals G₁and G₂have the same meaning as above; G₅represents a polymer residue resulting from the (homo)polymerization of at least one ethylenically unsaturated hydrophobic monomer or from the copolymerization of at least one ethylenically unsaturated anionic monomer and of at least one ethylenically unsaturated hydrophobic monomer; n is equal to 0 or 1; a is an integer ranging from 0 to 50; b is an integer that may-be between 10 and 350; on condition that a is other than 0.
The unit of formula (V) in the above text preferably has at least one, and even more preferably all, of the following characteristics:
the radicals G₁denote an alkyl radical, preferably a methyl radical;
n is not zero, and the radicals G₂represent a C₁-C₃divalent radical, preferably a propylene radical.
The number-average molecular mass of the silicone polymers with a polysiloxane skeleton grafted with non-silicone organic monomers of the invention preferably ranges from about 10 000 to 1 000 000 and even more preferably from about 10 000 to 100 000.
The composition may contain from 2% to 60% by weight, better still from 5% to 60% and preferably from 2% to 30% by weight of solids of film-forming polymer. More generally, the total amount of polymer should be an amount sufficient to form on the skin and/or the lips a cohesive film capable of following the movements of the skin and/or the lips without becoming detached or cracking.
When the polymer has a glass transition temperature that is too high for the desired use, a plasticizer may be combined therewith so as to lower this temperature of the mixture used. The plasticizer may be selected from the plasticizers usually used in the field of application, and especially from compounds that can be solvents for the polymer.
The composition according to the invention may comprise a hydrophilic medium comprising water or a mixture of water and hydrophilic organic solvent(s), for instance alcohols, and especially linear or branched lower monoalcohols having 2 to 5 carbon atoms, such as ethanol, isopropanol or n-propanol, and polyols such as glycerol, diglycerol, propylene glycol, sorbitol, pentylene glycol, and polyethylene glycols, or else C₂ethers and C₂-C₄aldehydes which are hydrophilic.
The water or mixture of water and hydrophilic organic solvents may be present in the composition according to the invention in an amount ranging from 0.1% to 99% by weight, relative to the total weight of the composition, and preferably from 10% to 80% by weight.
The composition according to the invention may comprise emulsifying surfactants, which are present particularly in a proportion ranging from 2% to 30% by weight, relative to the total weight of the composition, and better still from 5% to 15%. These surfactants may be selected from anionic and nonionic surfactants. Reference may be made to the document “Encyclopaedia of Chemical Technology, Kirk-Othmer”, volume 22, pp. 333-432, 3rd edition, 1979, Wiley, for the definition of the properties and functions (emulsifying) of the surfactants, especially pp. 347-77 of the said reference, for the anionic and nonionic surfactants.
The surfactants used preferentially in the composition according to the invention are selected:
from nonionic surfactants: fatty acids, fatty alcohols, polyethoxylated and polyglycerolated fatty alcohols, such as polyethoxylated stearyl or cetylstearyl alcohols, fatty acid esters of sucrose, alkyl glucose esters, especially the polyoxyethylenated fatty esters of C₁-C₆alkyl glucose, and mixtures thereof.
from anionic surfactants: C₁₆-C₃₀fatty acids neutralized with amines, aqueous ammonia or alkali metal salts, and mixtures thereof.
According to one embodiment it is preferred to use surfactants which allow an oil-in-water or wax-in-water emulsion to be obtained.
The composition according to the invention comprises an organic liquid medium which is cosmetically acceptable (acceptable tolerance, toxicology and feel).
According to one particularly preferred embodiment the organic liquid medium of the composition comprises at least one organic solvent, which is the, or one of the, polymerization solvent(s) of the block polymer as described above. Advantageously the said organic solvent is the majority liquid by weight in the organic liquid medium of the cosmetic composition.
According to one embodiment, the organic solvent medium comprises fatty substances which are liquid at ambient temperature (25° C. in general), called oils. These liquid fatty substances may be animal, vegetable, mineral or synthetic in origin.
As oils which can be used in the invention mention may be made of: hydrocarbon oils of animal origin, such as perhydrosqualene; vegetable hydrocarbon oils, such as liquid triglycerides of fatty acids of 4 to 10 carbon atoms, such as heptanoic or octanoic acid triglycerides, or else sunflower oil, corn oil, soya oil, grape seed oil, sesame oil, apricot oil, macadamia oil, castor oil, avocado oil, caprylic/capric acid triglycerides, jojoba oil, karite butter; linear or branched hydrocarbons, of mineral or synthetic origin, such as liquid paraffins and derivatives thereof, Vaseline, polydecenes, hydrogenated polyisobutene such as parleam; the synthetic esters and ethers particularly of fatty acids, such as, for example, purcellin oil, isopropyl myristate, 2-ethylhexyl palmitate, 2-octyldodecyl stearate, 2-octyldodecyl erucate, isostearyl isostearate; hydroxylated esters such as isostearyl lactate, octyl hydroxystearate, octyldodecyl hydroxystearate, diisostearyl malate, triisocetyl citrate, and heptanoates, octanoates and decanoates of fatty alcohols; polyol esters such as propylene glycol dioctanoate, neopentyl glycol diheptanoate and diethylene glycol diisononanoate; and pentaerythritol esters; fatty alcohols having 12 to 26 carbon atoms, such as octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, and oleyl alcohol; partially hydrocarbon-based and/or silicone-based fluoro oils; silicone oils, such as volatile or non-volatile polydimethylsiloxanes (PDMS) that are linear or cyclic, such as cyclomethicones, dimethicones, optionally including a phenyl group, such as phenyl trimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenylmethyldimethyltrisiloxanes, diphenyldimethicones, phenyldimethicones and polymethylphenylsiloxanes; and mixtures thereof.
These oils may be present in an amount ranging from 0.01% to 90%, and better still from 0.1% to 85% by weight, relative to the total weight of the composition.
The organic liquid medium of the composition according to the invention may also comprise one or more organic solvents which are cosmetically acceptable (acceptable tolerance, toxicology and feel).
These solvents may be generally present in an amount ranging from 0.1% to 90%, more preferably from 10% to 90% by weight, relative to the total weight of the composition, and better still from 30% to 90%.
As solvents which can be used in the composition of the invention mention may be made, besides the aforementioned hydrophilic organic solvents, of ketones which are liquid at ambient temperature, such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, isophorone, cyclohexanone and acetone; propylene glycol ethers which are liquid at ambient temperature, such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and dipropylene glycol mono-n-butyl ether; short-chain esters (having 3 to 8 carbon atoms in total), such as ethyl acetate, methyl acetate, propyl acetate, n-butyl acetate and isopentyl acetate; ethers which are liquid at ambient temperature, such as diethyl ether, dimethyl ether or dichlorodiethyl ether; alkanes which are liquid at ambient temperature, such as decane, heptane, dodecane, isododecane and cyclohexane; aromatic cyclic compounds which are liquid at ambient temperature, such as toluene and xylene; and aldehydes which are liquid at ambient temperature, such as benzaldehyde and acetaldehyde, and mixtures thereof.
The composition according to the invention may include at least one wax. By wax in the sense of the present invention is meant a lipophilic compound which is solid at ambient temperature (25° C.), exhibits a reversible solid/liquid state change and has a melting point greater than or equal to 30° C. and possibly up to 120° C.
The melting point of the wax can be measured by means of a differential scanning calorimeter (DSC), an example being the calorimeter sold under the name DSC 30 by the company Mettler.
The waxes may be hydrocarbon waxes, fluoro waxes and/or silicone waxes and may be vegetable, mineral, animal and/or synthetic in origin. In particular the waxes have a melting point of more than 25° C. and better still more than 45° C.
As wax which can be used in the composition of the invention mention may be made of beeswax, carnauba wax or candelilla wax, paraffin, microcrystalline waxes, ceresin or ozokerite; synthetic waxes such as polyethylene waxes or Fischer-Tropsch waxes, and silicone waxes such as the alkyl- or alkoxy-dimethicones having 16 to 45 carbon atoms.
The gums are generally high molecular weight polydimethylsiloxanes (PDMS) or cellulose gums or polysaccharides. The pasty substances are generally hydrocarbon compounds such as lanolins and their derivatives or else PDMS.
The nature and amount of the solid fatty substances are a function of the desired mechanical properties and textures. By way of indication the composition may contain from 0% to 50% by weight of waxes, relative to the total weight of the composition, and better still from 1% to 30% by weight. The polymer may be combined with one or more auxiliary film-forming agents. A film-forming agent of this kind may be selected from all of the compounds known to the person skilled in the art as being capable of fulfilling the desired function, and particularly may be selected from plasticizers and coalescers.
The composition according to the invention may further comprise one or more colorants selected from water-soluble dyes and pulverulent colorants such as pigments, nacres and flakes, which are well known to the person skilled in the art. The colorants may be present in the composition in an amount ranging from 0.01% to 50% by weight, relative to the weight of the composition, preferably from 0.01% to 30% by weight.
By pigments are meant particles of any form, white or coloured, organic or inorganic, which are insoluble in the physiological medium and are intended for colouring the composition.
By nacres are meant iridescent particles of any form that are produced in particular by certain molluscs in their shell, or else are synthesized.
The pigments may be white or coloured, organic and/or inorganic. Among inorganic pigments mention may be made of titanium dioxide, optionally in surface-treated form, zirconium oxide or cerium oxide, and also zinc oxide, iron oxides (black, yellow or red) or chromium oxide, manganese violet, ultramarine blue, chromium hydrate and ferric blue, and metal powders such as aluminium powder and copper powder.
Among organic pigments mention may be made of carbon black, D & C pigments, and the cochineal carmine-based lakes of barium, strontium, calcium and aluminium.
Mention may also be made of effect pigments, such as particles comprising an organic or inorganic, natural or synthetic substrate, for example glass, acrylic resins, polyester, polyurethane, polyethylene terephthalate, ceramics or aluminas, the said substrate being uncovered or covered with metallic substances such as aluminium, gold, silver, platinum, copper or bronze, or with metal oxides such as titanium dioxide, iron oxide or chromium oxide, and mixtures thereof.
The nacreous pigments may be selected from white nacreous pigments such as titanium-covered mica, or bismuth oxychloride, coloured nacreous pigments such as titanium mica covered with iron oxides, titanium mica covered with, in particular, ferric blue or chromium oxide, titanium mica covered with an organic pigment of the aforementioned type, and also nacreous pigments based on bismuth oxychloride. It is also possible to use interference pigments, especially those which are liquid-crystal pigments or multi-layer pigments.
The water-soluble dyes are, for example, beetroot juice and methylene blue.
The composition according to the invention may further comprise one or more fillers, particularly in an amount ranging from 0.01% to 50% by weight, relative to the total weight of the composition, preferably ranging from 0.01% to 30% by weight. By fillers are meant particles of any form, colourless or white, mineral or synthetic, which are insoluble in the medium of the composition irrespective of the temperature at which the composition is manufactured. These fillers serve in particular to modify the rheology or texture of the composition.
The fillers may be organic or inorganic and may be in any form, platelet-shaped, spherical or oblong, irrespective of the crystallographic form (for example leaf, cubic, hexagonal, orthorhombic, etc.). Mention may be made of talc, mica, silica, kaolin, polyamide (Nylon®) powders (Orgasol® from Atochem), poly-β-alanine and polyethylene, the powders of polymers of tetrafluoroethylene (Teflon®), lauroyl-lysine, starch, boron nitride, hollow polymeric microspheres such as those of polyvinylidene chloride/acrylonitrile, for instance Expancel® (Nobel Industrie), acrylic acid copolymers (Polytrap® from the company Dow Corning) and silicone resin microbeads (Tospearls® from Toshiba, for example), elastomeric polyorganosiloxane particles, precipitated calcium carbonate, magnesium carbonate and magnesium hydrocarbonate, hydroxyapatite, hollow silica microspheres (Silica Beads® from Maprecos), ceramic or glass microcapsules, metal soaps derived from organic carboxylic acids having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, for example zinc stearate, magnesium stearate or lithium stearate, zinc laurate and magnesium myristate.
The composition according to the invention may be in the form in particular of a stick, suspension, dispersion, solution, gel, emulsion, especially oil-in-water (O/W) or water-in-oil (W/O), or multiple (O/W/O or polyol/O/W or W/O/W), emulsion, or in the form of a cream, paste or mousse, or a vesicle dispersion, particularly of ionic or nonionic lipids, or a two-phase or multi-phase lotion, a spray, powder or paste, especially a flexible paste (in particular a paste having a dynamic viscosity at 25° C. of the order of 0.1 to 40 Pa·s at a shear rate of 200 s⁻¹, after 10 minutes of measurement in cone/plate geometry). The composition may be anhydrous: for example, it may be an anhydrous paste.
The person skilled in the art will be able to select the appropriate type of formulation, and the method of preparing it, on the basis of his or her general knowledge, taking into account, on the one hand, the nature of the constituents used, and especially their solubility in the vehicle, and, on the other hand, the application envisaged for the composition.
The composition according to the invention may be a makeup composition such as products for the complexion (foundations), rouges, eyeshadows, lipsticks, concealers, blushers, mascaras, eyeliners, eyebrow makeup products, lip pencils, eye pencils, nail products, such as nail varnishes, body makeup products or hair makeup products (hair lacquer or mascara).
The composition according to the invention may also be a facial or bodily skincare product, in particular a sun product or skin colouring product (such as a self-tanning product).
The composition according to the invention may also be a hair product, particularly a product for maintaining the hairstyle or the shaping of the hair. The hair compositions are preferably shampoos, gels, setting lotions, styling lotions, fixing compositions and styling compositions such as lacquers or sprays.
According to one embodiment the invention provides a coating composition for keratin fibres (such as the eyelashes, eyebrows and hair) comprising an organic liquid medium, at least one aqueous phase and at least one film-forming ethylenic linear block polymer and a dispersion of particles of film-forming polymer as described above.
Advantageously the water-dispersible film-forming polymer is selected from polyurethanes, polyurethane-acrylics, polyacrylics, poly(meth)acrylic esters, polyvinylpyrrolidones, polyurethane-polyvinylpyrrolidones, polyester-polyurethanes, polyether-polyurethanes, polyureas, polyurea/polyurethanes, and mixtures thereof as defined above.
Advantageously the composition comprises at least one second film former selected from water-soluble polymers such as cationic cellulose derivatives and/or optionally modified polymers of natural origin such as gum arabic.
Preferably the said composition comprises a wax, and more preferably it comprises a surfactant.
A composition of this kind may be present in a variety of forms: for example, in the form of two-phase wax-in-water or water-in-wax emulsions, or aqueous or anhydrous dispersions.
Advantageously the composition is a composition for coating the lashes, or mascara.
The present invention likewise provides a cosmetic kit comprising:
a container delimiting at least one compartment, the said container being closed by a closing element; and
a composition as described above disposed inside the said compartment.
The container may be in any appropriate form. It may in particular be in the form of a bottle, tube, jar, case, box, sachet or carton.
The closing element may be in the form of a removable stopper, a lid, a cap, a tear-off strip or a capsule, particularly of the type comprising a body attached to the container and a cover cap articulated on the body. It may also be in the form of an element for selectively closing the container, particularly a pump, valve or valve flap.
The container may be combined with an applicator, particularly in the form of a brush comprising an arrangement of bristles held by a twisted wire. A twisted brush of this kind is described in particular in patent U.S. Pat. No. 4,887,622. It may also be in the form of a comb comprising a plurality of application elements, obtained in particular from moulding. Combs of this kind are described, for example, in patent FR 2 796 529. The applicator may be in the form of a fine brush, as described, for example, in patent FR 2 722 380. The applicator may be in the form of a block of foam or elastomer, a felt or a spatula. The applicator may be free (tuft or sponge) or of one piece with a rod carried by the closing element, as described, for example, in patent U.S. Pat. No. 5,492,426. The applicator may be of one piece with the container, as described, for example, by patent FR 2 761 959.
The product may be accommodated directly in the container, or indirectly. By way of example, the product may be arranged on an impregnated support, particularly in the form of a wipe or pad, and arranged (in unitary or plural form) in a box or in a sachet. A support of this kind, incorporating the product, is described for example in patent application WO 01/03538.
The closing element may be coupled to the container by screwing. Alternatively the coupling between the closing element and the container is performed other than by screwing, in particular via a bayonet mechanism, by snap-fastening, gripping, welding, adhesive bonding, or by magnetic attraction. By “snap-fastening” is meant, in particular, any system involving the traversal of a bead or cord of material by elastic deformation of a portion, particularly of the closing element, followed by return to the elastically unstressed position of the said portion after the traversal of the bead or cord.
The container may be at least partly made of thermoplastic material. Examples that may be mentioned of thermoplastic materials include polypropylene and polyethylene.
Alternatively the container is made of a non-thermoplastic material, particularly of glass or of metal (or alloy).
The container may be one with rigid walls or may have deformable walls, particularly in the form of a tube or tubular bottle.
The container may include means intended for distributing, or facilitating the distribution of, the composition. By way of example, the container may have walls which are deformable so as to allow the composition to exit in response to a positive pressure inside the container, this positive pressure being brought about by elastic (or non-elastic) squeezing of the container's walls. Alternatively, and particularly when the product is in the form of a stick, the product may be driven by a piston mechanism. Still in the case of a stick, particularly a makeup product stick (lipstick, foundation, etc.), the container may include a mechanism, especially a rack mechanism, or one with a threaded rod, or with a helical groove, which is capable of displacing a stick in the direction of the said opening. A mechanism of this kind is described for example in patent FR 2 806 273 or in patent FR 2 775 566. A mechanism of this kind for a liquid product is described in patent FR 2 727 609.
The container may be composed of a carton with a base delimiting at least one housing accommodating the composition, and a lid, particularly a lid articulated on the base, which is capable of covering the said base, at least in part. A carton of this kind is described for example in patent application WO 03/018423 or in patent FR 2 791 042.
The container may be equipped with a drainer arranged in the region of the opening of the container. A drainer of this kind allows the applicator to be wiped and optionally allows the rod, which may be of one piece with it, to be wiped. A drainer of this kind is described for example in patent FR 2 792 618.
The composition may be at the atmospheric pressure inside the container (at ambient temperature) or may be in pressurized form, particularly by means of a propellent gas (aerosol). In the latter case the container is equipped with a valve (of the type used for aerosols).
The content of the patents or patent applications cited above is incorporated by reference into the present application.
The examples which follow illustrate, without limitation, the compositions according to the invention.

EXAMPLE 4

Liquid Lipstick



	INGREDIENTS	% BY MASS

	Polymer from Example 2	50.0
	Silica (Aerosil R 972 ®, Degussa)	5.0
	Isododecane gelled with an ethylene/	7.0
	propylene/styrene copolymer and a
	butylene/ethylene/styrene copolymer
	(Versagel ® MD 970, Penreco)
	Hydrogenated polyisobutene	2.1
	Octyldodecanol	0.9
	Phenyltrimethicone (DC 556, 20 cSt, Dow	2.1
	Corning)
	Isododecane	28.3
	Vinylpyrrolidone/1-eicosene copolymer	1.2
	(Antaron V-220 ®, ISP)
	Pigments	3.0
	Perfume	qs

It can also be applied without difficulty using a foam applicator, and leads to a homogeneous deposit with good staying power.

EXAMPLE 5

Sun Composition



Ingredients	(% by weight)

Glycerol	6
Propylene glycol	6
Acrylates/C₁₀-C₃₀alkyl acrylate copolymer	0.3
PEMULEN TR-2 (Noveon)
Ammonium polyacryloyldimethyltaurate polymer	0.3
(HOSTACERIN AMPS - Clariant)
Cyclohexasiloxane (DOW CORNING 246 FLUID - Dow	6
Corning)
Xanthan gum RHODICARE XC (Rhodia)	0.1
Terephthalylidene dicamphor sulphonic acid	1.5
(MEXORYL SX - Chimex)
Triethanolamine	qs
Octocrylene (UVINUL N539 - BASF)	10
Butylmethoxydibenzoylmethane (Parsol 1789 -	2.5
Roche Vitamines)
Drometrizole trisiloxane (MEXORYL XL - Chimex)	1.5
C₁₂-C₁₅alkyl benzoate (FINSOLV TN - Witco)	4
Polymer from Example 1	1
Triethanolamine	0.35
Preservative and sequestrant	qs
Water	qs 100

EXAMPLES 6 to 11

Emulsion Mascaras

The following mascara compositions were prepared according to the invention and the prior art:
The prior art composition of Example 6 contains neither block polymer nor aqueous dispersion of particles of film-forming polymer.
The composition of Example 10 includes an aqueous dispersion of particles of film-forming polymer, but no block polymer.

The compositions of Examples 7 to 9 and 11, according to the invention, include a block polymer and an aqueous dispersion of particles of film-forming polymer.



Example 6	Example 7	Example 8	Example 9	Example 10	Example 11
(comparative)	(inventive)	(inventive)	(inventive)	(comparative)	(inventive)

Candelilla wax	20	5	5	5	5
Aqueous polyurethane		8.3 (AS*)
dispersion containing 38% AS
(“Avalure UR-450 ®” from the
company Goodrich)
Ethyl acrylate/methyl			10 (AS)
methacrylate (80/20)
copolymer in aqueous
dispersion containing 50% AS
(“Daltosol 5000 AD ®” from
DAITO)
Acrylic and styrene/acrylic				8.7 (AS)	17.42 (AS)	6.37 (AS)
copolymer in aqueous
dispersion containing 40% AS
(“Syntran 5760” from the
company Interpolymer)
Block polymer from Example 3		10 (AS)	10 (AS)	10 (AS)		15 (AS)

Stearic acid	5.8
Triethanolamine stearate	2.9
Black iron oxide	8
Hydroxyethylcellulose	0.9
Gum arabic	3.4
Water, preservatives	qs 100

*AS: active substance

For each composition, the dry extract, the load in vitro and the staying power are measured, according to the methods described below.
The load in vitro is measured by gravimetry on specimens of curled Caucasian hair (30 hairs, 1 cm long, distributed over a distance of 1 cm).
The specimen is made up by carrying out 3×10 passages of mascara spaced apart by 2 minutes, with collection of product between each series of 10.
The specimen is dried at ambient temperature for 10 minutes and then weighed.
This measurement is carried out on 6 specimens.
The load is the amount of material deposited on the specimen=mass of made-up specimen−mass of bare specimen.
The average load is the mean of the measurements carried out on the 6 specimens.
The solids content, in other words the amount of non-volatile material, or dry extract of the compositions is measured on a Mettler Toledo HG 53 balance (Halogen Moisture Analyzer). A sample of mascara (2-3 g) is placed on an aluminium boat and subjected to a temperature of 120° C. for 60 minutes. The dry extract measurement corresponds to the monitoring of the mass of the sample over time. The final solids content is therefore the percentage of the final mass (after 60 minutes) relative to the initial mass: SC=(final mass/initial mass)×100.
The staying power of the film formed by the composition according to the invention is evaluated by measuring the water resistance, over time, of a film of composition spread onto a glass plate and subjected to stirring in aqueous medium. The protocol is as follows:
At ambient temperature (25° C.) a layer of composition 300 μm thick (before drying) with a surface area of 9 cm×9 cm is spread over a glass plate with a surface area of 10 cm×10 cm, and then left to dry at 30° C. and 50% relative humidity for 24 hours. After drying, the plate is placed in a 2-litre crystallizer with a diameter of 19 cm, which is filled with one litre of water and placed on a heating magnetic stirrer sold under the name RCT basic by the company IKA labortechnik. A smooth cylindrical magnetic PTFE bar (length 6 cm; diameter 1 cm) is then placed on the film. The stirring speed is set to position 5. The water temperature is regulated by means of a thermometer to a temperature of 20° C. or 40° C. At time t₀=0, stirring is commenced. A measurement is made of the time t (expressed in minutes) after which the film begins to detach or disbond from the plate or when a hole the size of the magnetic stirring bar is observed, in other words when the hole has a diameter of 6 cm.
The water resistance of the film corresponds to the measured time t.

The results obtained are as follows:

Measured solids content	38.8	43.8	45.2	44.9	41.6	41.8
(%)
Load in vitro (mg)		11.90 ± 1.34	12.5 ± 1.42	10.18 ± 1.54	7.43 ± 0.65	11.17 ± 0.74
Staying power	55″	1′24″	2′24″	6′26″	38′	19′

It is found that the compositions according to the invention, of Examples 7 to 9 and 11, comprising the combination of an aqueous dispersion of particles of film-forming polymer and a block polymer, exhibit a good staying power, better than that of the composition of Example 10 which does not contain block polymer. Moreover, the compositions according to the invention allow the lashes to be made up thickly, since they have a high solids content and high levels of load in vitro.

EXAMPLE 12

Waterproof Mascara

The following mascara, according to the invention, was prepared:



	Carnauba wax	4.7
	Beeswax	8.2
	Rice bran wax	2.2
	Modified hectorite (“Bentone 38V ®” from	5.5
	Elementis)
	Paraffin wax	2.2
	Talc	1
	Vinyl acetate/allyl stearate copolymer	6.7
	(Mexomere PQ from the company Chimex)
	Block polymer from Example 1	10
	Polyvinyl laurate (Mexomere PP from the	0.7
	company Chimex)
	Sulphopolyester (Eastman AQ 55S from	0.1
	Eastman)
	Preservatives	0.2
	Propylene carbonate	1.8
	Water	7
	Pigments	5.2
	Isododecane	qs 100

Measurements were made of the solids content, the load in vitro and the staying power, according to the measurement methods described above in the description.
The following results were obtained:

Measured solids content (%) 45.4

Load in vitro (mg) 8.9 ± 0.9

Staying power Greater than one day (24 h)
This mascara exhibits good staying power while having a good thickening (loading) effect on the lashes.

Claims

1. Cosmetic composition comprising an organic liquid medium, at least one film-forming ethylenic linear block polymer free from styrene units, and at least one other film former which is soluble or dispersible in the said organic liquid medium.

2. Cosmetic composition comprising an organic liquid medium, at least one aqueous phase, at least one film-forming ethylenic linear block polymer free from styrene units, and at least one other film former which is soluble or dispersible in the said aqueous phase.

3. Cosmetic composition according to claim 1 or 2, characterized in that the block polymer is non-elastomeric.

4. Cosmetic composition according to one of the preceding claims, characterized in that the block polymer is an ethylenic polymer obtained from aliphatic ethylenic monomers comprising a carbon-carbon double bond and at least one ester group —COO— or amide group —CON—.

5. Cosmetic composition according to one of the preceding claims, characterized in that the polymer is not soluble at an amount of active substance of at least 1% by weight in water or in a mixture of water and linear or branched lower monoalcohols having 2 to 5 carbon atoms, without a change in pH, at ambient temperature (25° C.).

6. Cosmetic composition according to one of the preceding claims, characterized in that the block polymer contains first and second blocks connected to one another by an intermediate segment comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block.

7. Cosmetic composition according to one of the preceding claims, characterized in that the block polymer comprises first and second blocks having different glass transition temperatures (Tgs).

8. Composition according to the preceding claim, characterized in that the first and second blocks are connected to one another by an intermediate segment having a glass transition temperature between the glass transition temperatures of the first and second blocks.

9. Cosmetic composition according to one of the preceding claims, characterized in that the block polymer comprises first and second blocks which are incompatible in the said organic liquid medium.

10. Cosmetic composition according to one of the preceding claims, characterized in that the block polymer has a polydispersity index I of greater than 2.

11. Composition according to claim 7, characterized in that the first block of the polymer is selected from:

a) a block with a Tg of greater than or equal to 40° C.,

b) a block with a Tg of less than or equal to 20° C.,

c) a block with a Tg between 20 and 40° C., and

the second block is selected from a category a), b) or c) different from the first block.

12. Composition according to claim 11, characterized in that the block with a Tg of greater than or equal to 40° C. is obtained totally or partly from one or more monomers which are such that the homopolymer prepared from these monomers has a glass transition temperature of greater than or equal to 40° C.

13. Composition according to the preceding claim, characterized in that the monomers whose corresponding homopolymer has a glass transition temperature of greater than or equal to 40° C. are selected from the following monomers:

methacrylates of formula CH₂═C(CH₃)—COOR₁in which R₁represents a linear or branched unsubstituted alkyl group containing from 1 to 4 carbon atoms, such as a methyl, ethyl, propyl or isobutyl group, or R₁represents a C₄to C₁₂cycloalkyl group;

acrylates of formula CH₂═CH—COOR₂in which R₂represents a C₄to C₁₂cycloalkyl group, such as isobornyl acrylate or a tert-butyl group;

(meth)acrylamides of formula:

where R₇and R₈, which are identical or different, each represent a hydrogen atom or a linear or branched alkyl group having from 1 to 12 carbon atoms, such as an n-butyl, t-butyl, isopropyl, isohexyl, isooctyl or isononyl group; or R₇represents H and R₈represents a 1,1-dimethyl-3-oxobutyl group and R′ denotes H or methyl;

and mixtures thereof.

14. Composition according to claim 12 or 13, characterized in that the monomers whose corresponding homopolymer has a glass transition temperature of greater than or equal to 40° C. are selected from methyl methacrylate, isobutyl(meth)acrylate, isobornyl(meth)acrylate, and mixtures thereof.

15. Composition according to claim 11, characterized in that the block with a Tg of less than or equal to 20° C. is obtained totally or partly from one or more monomers which are such that the homopolymer prepared from these monomers has a glass transition temperature of less than or equal to 20° C.

16. Composition according to claim 15, characterized in that the monomers whose corresponding homopolymer has a glass transition temperature of less than or equal to 20° C. are selected from the following monomers:

acrylates of formula CH₂═CHCOOR₃, R₃representing a linear or branched C₁to C₁₂unsubstituted alkyl group, with the exception of the tert-butyl group, in which one or more heteroatoms selected from O, N and S is (are) optionally intercalated;

methacrylates of formula CH₂═C(CH₃)—COOR₄, R₄representing a linear or branched C₆to C₁₂unsubstituted alkyl group, in which one or more hetero-atoms selected from O, N and S is (are) optionally intercalated;

vinyl esters of formula R₅—CO—O—CH═CH₂where R₅represents a linear or branched C₄to C₁₂alkyl group;

C₄to C₁₂alkyl vinyl ethers;

N—(C₄to C₁₂alkyl) acrylamides, such as N-octylacrylamide;

and mixtures thereof.

17. Composition according to claim 15 or 16, characterized in that the monomers whose corresponding homopolymer has a glass transition temperature of less than or equal to 20° C. are selected from alkyl acrylates in which the alkyl chain contains from 1 to 10 carbon atoms, with the exception of the tert-butyl group.

18. Composition according to claim 11, characterized in that the block with a Tg of between 20 and 40° C. is obtained totally or partly from one or more monomers which are such that the homopolymer prepared from these monomers has a glass transition temperature of between 20 and 40° C.

19. Composition according to claim 11, characterized in that the block with a Tg of between 20 and 40° C. is obtained totally or partly from monomers which are such that the corresponding homopolymer has a Tg of greater than or equal to 40° C. and from monomers which are such that the corresponding homopolymer has a Tg of less than or equal to 20° C.

20. Composition according to claim 18 or 19, characterized in that the block with a Tg of between 20 and 40° C. is obtained totally or partly from monomers selected from methyl methacrylate, isobornyl acrylate and methacrylate, butyl acrylate, 2-ethylhexyl acrylate, and mixtures thereof.

21. Composition according to one of claims 11 to 20, characterized in that it comprises a block polymer comprising at least one first block and at least one second block, the first block having a glass transition temperature (Tg) of greater than or equal to 40° C. and the second block having a glass transition temperature of less than or equal to 20° C.

22. Composition according to the preceding claim, characterized in that the first block is obtained totally or partly from one or more monomers which are such that the homopolymer prepared from these monomers has a glass transition temperature of greater than or equal to 40° C.

23. Composition according to claim 22, characterized in that the first block is a copolymer obtained from monomers which are such that the homopolymer prepared from these monomers has a glass transition temperature of greater than or equal to 40° C.

24. Composition according to claim 22 or 23, characterized in that the monomers whose corresponding homopolymer has a glass transition temperature of greater than or equal to 40° C. are selected from the following monomers:

(meth)acrylamides of formula:

and mixtures thereof.

25. Composition according to one of claims 22 to 24, characterized in that the monomers whose corresponding homopolymer has a glass transition temperature of greater than or equal to 40° C. are selected from methyl methacrylate, isobutyl methacrylate, isobornyl(meth)acrylate, and mixtures thereof.

26. Composition according to one of claims 22 to 25, characterized in that the proportion of the first block ranges from 20% to 90%, more preferably from 30% to 80% and better still from 50% to 70% by weight of the polymer.

27. Composition according to one of claims 21 to 26, characterized in that the second block is obtained totally or partly from one or more monomers which are such that the homopolymer prepared from these monomers has a glass transition temperature of less than or equal to 20° C.

28. Composition according to one of claims 21 to 27, characterized in that the second block is a homopolymer obtained from monomers which are such that the homopolymer prepared from these monomers has a glass transition temperature of less than or equal to 20° C.

29. Composition according to claim 27 or 28, characterized in that the monomers whose corresponding homopolymer has a glass transition temperature of less than or equal to 20° C. are selected from the following monomers:

C₄to C₁₂alkyl vinyl ethers;

N—(C₄to C₁₂alkyl) acrylamides, such as N-octylacrylamide;

and mixtures thereof.

30. Composition according to one of claims 27 to 29, characterized in that the monomers whose corresponding homopolymer has a glass transition temperature of less than or equal to 20° C. are selected from alkyl acrylates in which the alkyl chain contains from 1 to 10 carbon atoms, with the exception of the tert-butyl group.

31. Composition according to one of claims 21 to 30, characterized in that the proportion of the second block with a Tg of less than or equal to 20° C. ranges from 5% to 75% by weight of the polymer, better still from 15% to 50% and even better still from 25% to 45%.

32. Composition according to one of claims 11 to 20, characterized in that it comprises a block polymer comprising at least one first block and at least one second block, the first block having a glass transition temperature (Tg) of between 20 and 40° C. and the second block having a glass transition temperature of less than or equal to 20° C. or a glass transition temperature of greater than or equal to 40° C.

33. Composition according to the preceding claim, characterized in that the first block with a Tg of between 20 and 40° C. is obtained totally or partly from one or more monomers which are such that the homopolymer prepared from these monomers has a glass transition temperature of between 20 and 40° C.

34. Composition according to claim 32 or 33, characterized in that the first block with a Tg of between 20 and 40° C. is a copolymer obtained from monomers which are such that the corresponding homopolymer has a Tg of greater than or equal to 40° C. and from monomers which are such that the corresponding homopolymer has a Tg of less than or equal to 20° C.

35. Composition according to one of claims 32 to 34, characterized in that the first block with a Tg of between 20 and 40° C. is obtained from monomers selected from methyl methacrylate, isobornyl acrylate and methacrylate, butyl acrylate, 2-ethylhexyl acrylate, and mixtures thereof.

36. Composition according to one of claims 32 to 35, characterized in that the proportion of the first block with a Tg of between 20 and 40° C. ranges from 10% to 85%, better still from 30% to 80% and even better still from 50% to 70% by weight of the polymer.

37. Composition according to any one of claims 32 to 35, characterized in that the second block has a Tg of greater than or equal to 40° C. and is obtained totally or partly from one or more monomers which are such that the homopolymer prepared from these monomers has a glass transition temperature of greater than or equal to 40° C.

38. Composition according to any one of claims 32 to 37, characterized in that the second block has a Tg of greater than or equal to 40° C. and is a homopolymer obtained from monomers which are such that the homopolymer prepared from these monomers has a glass transition temperature of greater than or equal to 40° C.

39. Composition according to either of claims 37 and 38, characterized in that the monomers whose corresponding homopolymer has a glass transition temperature of greater than or equal to 40° C. are selected from the following monomers:

(meth)acrylamides of formula:

and mixtures thereof.

40. Composition according to one of claims 36 to 39, characterized in that the monomers whose corresponding homopolymer has a glass transition temperature of greater than or equal to 40° C. are selected from methyl methacrylate, isobutyl methacrylate, isobornyl(meth)acrylate, and mixtures thereof.

41. Composition according to one of claims 37 to 40, characterized in that the proportion of the second block with a Tg of greater than or equal to 40° C. ranges from 10% to 85%, preferably from 20% to 70% and better still from 30% to 70% by weight of the polymer.

42. Composition according to any one of claims 32 to 41, characterized in that the second block has a Tg of less than or equal to 20° C. and is obtained totally or partly from one or more monomers which are such that the homopolymer prepared from these monomers has a glass transition temperature of less than or equal to 20° C.

43. Composition according to any one of claims 32 to 41, characterized in that the second block has a Tg of less than or equal to 20° C. and is a homopolymer obtained from monomers which are such that the homopolymer prepared from these monomers has a glass transition temperature of less than or equal to 20° C.

44. Composition according to claim 42 or 43, characterized in that the monomers whose corresponding homopolymer has a glass transition temperature of less than or equal to 20° C. are selected from the following monomers:

C₄to C₁₂alkyl vinyl ethers;

N—(C₄to C₁₂alkyl) acrylamides, such as N-octylacrylamide;

and mixtures thereof.

45. Composition according to one of claims 42 to 44, characterized in that the monomers whose corresponding homopolymers have glass transition temperatures of less than or equal to 20° C. are selected from alkyl acrylates in which the alkyl chain contains from 1 to 10 carbon atoms, with the exception of the tert-butyl group.

46. Composition according to one of claims 42 to 45, characterized in that the proportion of the block with a glass transition temperature of greater than or equal to 40° C. ranges from 20% to 90% by weight of the polymer, better still from 30% to 80% and even better still from 50% to 70%.

47. Cosmetic composition according to one of claims 6 to 8 or any of the preceding claims appendant thereto, characterized in that the first block and/or the second block comprises at least one additional monomer.

48. Composition according to the preceding claim, characterized in that the additional monomer is selected from hydrophilic monomers and ethylenically unsaturated monomers comprising one or more silicon atoms, and mixtures thereof.

49. Composition according to claim 47 or 48, characterized in that the additional monomer is selected from:

a) hydrophilic monomers such as:

ethylenically unsaturated monomers comprising at least one carboxylic or sulphonic acid function, for instance:

acrylic acid, methacrylic acid, crotonic acid, maleic anhydride, itaconic acid, fumaric acid, maleic acid, acrylamidopropanesulphonic acid, vinylbenzoic acid, vinylphosphoric acid, and salts thereof;

ethylenically unsaturated monomers comprising at least one tertiary amine function, for instance 2-vinylpyridine, 4-vinylpyridine, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate and dimethylaminopropylmethacrylamide, and salts thereof;

methacrylates of formula CH₂═C(CH₃)—COOR₆in which R₆represents a linear or branched alkyl group containing from 1 to 4 carbon atoms, such as a methyl, ethyl, propyl or isobutyl group, the said alkyl group being substituted by one or more substituents selected from hydroxyl groups (for instance 2-hydroxypropyl methacrylate and 2-hydroxyethyl methacrylate) and halogen atoms (Cl, Br, I or F), such as trifluoroethyl methacrylate;

methacrylates of formula CH₂═C(CH₃)—COOR₉, R₉representing a linear or branched C₆to C₁₂alkyl group in which one or more heteroatoms selected from O, N and S is (are) optionally intercalated, the said alkyl group being substituted by one or more substituents selected from hydroxyl groups and halogen atoms (Cl, Br, I or F);

acrylates of formula CH₂═CHCOOR₁₀, R₁₀representing a linear or branched C₁to C₁₂alkyl group substituted by one or more substituents selected from hydroxyl groups and halogen atoms (Cl, Br, I or F), such as 2-hydroxypropyl acrylate and 2-hydroxyethyl acrylate, or R₁₀represents a C₁to C₁₂alkyl-O-POE (polyoxyethylene) with repetition of the oxyethylene unit from 5 to 30 times, for example methoxy-POE, or R₁₀represents a polyoxyethylenated group comprising from 5 to 30 ethylene oxide units; and

b) ethylenically unsaturated monomers comprising one or more silicon atoms, such as methacryloxypropyltrimethoxysilane and methacryloxy-propyltris(trimethylsiloxy)silane;

and mixtures thereof.

50. Composition according to either of claims 47 and 48, characterized in that each of the first and second blocks comprises at least one additional monomer selected from acrylic acid, (meth)acrylic acid, trifluoroethyl methacrylate, and mixtures thereof.

51. Composition according to either of claims 47 and 48, characterized in that each of the first and second blocks comprises at least one monomer selected from esters of (meth)acrylic acid and optionally at least one additional monomer such as (meth)acrylic acid, and mixtures thereof.

52. Composition according to either of claims 47 and 48, characterized in that each of the first and second blocks is obtained totally from at least one monomer selected from esters of (meth)acrylic acid and optionally at least one additional monomer such as (meth)acrylic acid, and mixtures thereof.

53. Composition according to one of claims 47 to 52, characterized in that the additional monomer or monomers represent(s) from 1% to 30% by weight of the total weight of the first and/or second blocks.

54. Composition according to claim 7 or any of the preceding claims appendant thereto, characterized in that the difference between the glass transition temperatures (Tg) of the first and second blocks is greater than 10° C., better still greater than 20° C., very preferably greater than 30° C. and better still greater than 40° C.

55. Composition according to claim 10, characterized in that the block polymer has a polydispersity index of greater than or equal to 2.5, preferably greater than or equal to 2.8.

56. Composition according to claim 55, characterized in that it has a polydispersity index of between 2.8 and 6.

57. Composition according to one of the preceding claims, characterized in that the block polymer has a weight-average mass (Mw) of less than or equal to 300 000.

58. Composition according to claim 57, characterized in that the weight-average mass (Mw) ranges from 35 000 to 200 000 and better still from 45 000 to 150 000.

59. Composition according to claim 58, characterized in that the weight-average mass (Mw) is less than or equal to 70 000.

60. Composition according to one of claims 57 to 59, whose weight-average mass (Mw) ranges from 10 000 to 60 000 and better still from 12 000 to 50 000.

61. Composition according to one of the preceding claims, characterized in that it contains from 0.1% to 60% by weight of polymer active substance, preferably from 5% to 50% by weight, and more preferably from 10% to 40% by weight.

62. Composition according to claim 1, characterized in that the film former is a film-forming polymer which is soluble in the said organic liquid medium.

63. Composition according to claim 62, characterized in that the film former is a fat-soluble film-forming polymer.

64. Composition according to claim 63, characterized in that the fat-soluble film-forming polymer is selected from the fat-soluble, amorphous homopolymers and copolymers of olefins, of cycloolefins, of butadiene, of isoprene, of styrene, of vinyl ethers, esters or of amides, or of (meth)acrylic acid esters or amides comprising a linear, branched or cyclic C_4-50alkyl group, which are preferably amorphous.

65. Composition according to claim 63, characterized in that the fat-soluble film-forming polymer is selected from homopolymers and copolymers obtained from monomers selected from the group consisting of isooctyl(meth)acrylate, isononyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, lauryl(meth)acrylate, isopentyl(meth)acrylate, n-butyl(meth)acrylate, isobutyl(meth)acrylate, methyl(meth)acrylate, tert-butyl(meth)acrylate, tridecyl(meth)acrylate, stearyl(meth)acrylate, or mixtures thereof, especially an alkyl acrylate/cycloalkyl acrylate copolymer and vinylpyrrolidone/decadecene copolymers.

66. Composition according to claim 63, characterized in that the fat-soluble film-forming polymer is selected from amorphous and fat-soluble polycondensates, preferably not comprising any groups donating hydrogen interactions, in particular polyesters having C_4-50alkyl side chains or else polyesters resulting from the condensation of fatty acid dimers, or even polyesters comprising a silicone-based segment in the form of a block, graft or end group, which is solid at ambient temperature.

67. Composition according to claim 63, characterized in that the fat-soluble film-forming polymer is selected from amorphous and fat-soluble polysaccharides comprising alkyl (ether or ester) side chains, in particular ethylcellulose, or silicone-acrylic graft polymers having a silicone skeleton and acrylic grafts or having an acrylic skeleton and silicone grafts.

68. Composition according to claim 63, characterized in that the fat-soluble film-forming polymer bears fluoro groups.

69. Composition according to claim 68, characterized in that the fat-soluble film-forming polymer is selected from alkyl(meth)acrylate/perfluoroalkyl(meth)acrylate copolymers.

70. Composition according to claim 63, characterized in that the fat-soluble film-forming polymer is selected from polymers or copolymers resulting from the polymerization or copolymerization of an ethylenic monomer comprising one or more ethylenic, preferably conjugated, bonds.

71. Composition according to claim 70, characterized in that the polymer or copolymer resulting from the polymerization or copolymerization of an ethylenic monomer is selected from polystyrene/copoly(ethylene/butylene)s.

72. Composition according to claim 63, characterized in that the fat-soluble film-forming polymer is selected from polymers containing a non-silicone organic skeleton grafted with monomers containing a polysiloxane.

73. Composition according to claim 63, in which the said at least one fat-soluble film-forming polymer is selected from silicone polymers grafted with non-silicone organic monomers.

74. Composition according to claim 1, characterized in that the film former is a film-forming polymer which is dispersible in the said organic liquid medium.

75. Composition according to claim 74, characterized in that the organic liquid medium comprises at least one oil, in that the film former is dispersible in the said oil and in that the film former is in the form of a non-aqueous dispersion of polymer particles.

76. Composition according to claim 2, characterized in that the film former is a film-forming polymer which is dispersible in the aqueous phase.

77. Composition according to claim 76, characterized in that the water-dispersible film-forming polymer is selected from polyurethanes, polyurethane-acrylics, polyurethane-polyvinyl-pyrrolidones, polyester-polyurethanes, polyether-polyurethanes, polyureas, polyurea/polyurethanes, and mixtures thereof.

78. Composition according to claim 77, characterized in that the water-dispersible film-forming polymer is an aliphatic, cycloaliphatic or aromatic polyurethane copolymer, or a polyurea/polyurethane or polyurea copolymer comprising, alone or as a mixture:

at least one block of linear or branched aliphatic and/or cycloaliphatic and/or aromatic polyester origin, and/or

at least one block of aliphatic and/or cycloaliphatic and/or aromatic polyether origin, and/or

at least one substituted or unsubstituted, branched or unbranched silicone block, for example polydimethylsiloxane or polymethylphenylsiloxane, and/or

at least one block comprising fluoro groups.

79. Composition according to claim 76, characterized in that the film-forming polymer which is dispersible in the aqueous phase is selected from polyesters, polyesteramides, fatty-chain polyesters, polyamides and epoxy ester resins.

80. Composition according to claim 76, characterized in that the film-forming polymer dispersible in the aqueous phase is selected from acrylic polymers, acrylic copolymers and vinyl polymers.

81. Composition according to claim 1, characterized in that the proportion of film former ranges from 2% to 60%, preferably from 5% to 60%, more preferably from 2% to 30% by weight of dry compound relative to the total weight of the composition.

82. Cosmetic composition according to any one of the preceding claims, characterized in that it further comprises one or more colorants selected from water-soluble dyes and pulverulent colorants such as pigments, nacres and flakes.

83. Cosmetic composition according to any one of the preceding claims, characterized in that it is in the form of a suspension, dispersion, solution, gel, emulsion, especially oil-in-water (O/W) or water-in-oil (W/O), or multiple (W/O/W or polyol/O/W or O/W/O), emulsion, or in the form of a cream, paste or mousse, or a vesicle dispersion, particularly of ionic or nonionic lipids, or a two-phase or multi-phase lotion, a spray, powder or paste, especially a flexible paste or anhydrous paste, or a stick or cast solid.

84. Cosmetic composition according to any one of the preceding claims, characterized in that it is in anhydrous form.

85. Cosmetic composition according to any one of the preceding claims, characterized in that it is a composition for making up or caring for keratin materials.

86. Composition according to one of the preceding claims, characterized in that it is a lip makeup product.

87. Composition according to one of the preceding claims, characterized in that it is an eye makeup product.

88. Composition according to one of the preceding claims, characterized in that it is a complexion makeup product.

89. Composition according to one of the preceding claims, characterized in that it is a nail makeup product.

90. Coating composition for keratin fibres, particularly the eyelashes and eyebrows, comprising an organic liquid medium, at least one aqueous phase, at least one film-forming ethylenic linear block polymer and at least one other film former soluble or dispersible in the said aqueous phase.

91. Composition according to one of the preceding claims, characterized in that the block polymer is in accordance with one of claims 1 to 61.

92. Composition according to claim 90 or 91, characterized in that the film former is a film-forming polymer dispersible in the aqueous phase.

93. Composition according to claim 92, characterized in that the water-dispersible film-forming polymer is selected from polyurethanes, polyurethane-acrylics, polyurethane-polyvinyl-pyrrolidones, polyester-polyurethanes, polyether-polyurethanes, polyureas, polyurea/polyurethanes, and mixtures thereof.

94. Composition according to one of claims 90 to 93, characterized in that it comprises a wax.

95. Composition according to one of claims 90 to 94, characterized in that it comprises a surfactant.

96. Composition according to one of claims 90 to 95, characterized in that it comprises at least one second film former selected from water-soluble polymers.

97. Composition according to the preceding claim, characterized in that the water-soluble polymer or polymers is or are selected from cationic cellulose derivatives and/or optionally modified polymers of natural origin such as gum arabic.

98. Composition according to one of claims 90 to 97, characterized in that it comprises a colorant.

99. Composition according to one of claims 90 to 98, characterized in that it is a mascara.

100. Cosmetic kit comprising:

a) a container delimiting at least one compartment, the said container being closed by a closing element; and

b) a composition disposed inside the said compartment, the composition being in accordance with any one of the preceding claims.

101. Cosmetic kit according to claim 100, characterized in that the container is formed, at least partly, of at least one thermoplastic material.

102. Cosmetic kit according to claim 100, characterized in that the container is formed, at least partly, of at least one non-thermoplastic material, particularly of glass or of metal.

103. Kit according to any one of claims 100 to 102, characterized in that, in the closed position of the container, the closing element is screwed onto the container.

104. Kit according to any one of claims 100 to 102, characterized in that, in the closed position of the container, the closing element is coupled to the container other than by screwing, in particular by snap fastening, adhesive bonding or welding.

105. Kit according to any one of claims 100 to 104, characterized in that the composition is substantially at the atmospheric pressure inside the compartment.

106. Kit according to any one of claims 100 to 104, characterized in that the composition is pressurized inside the container.

107. Cosmetic method of making up or caring for keratin materials, comprising the application to the keratin materials of a cosmetic composition according to one of claims 1 to 99.